CN116476466A - Metal foil for hydrogen purification and preparation method thereof - Google Patents
Metal foil for hydrogen purification and preparation method thereof Download PDFInfo
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- CN116476466A CN116476466A CN202310058359.3A CN202310058359A CN116476466A CN 116476466 A CN116476466 A CN 116476466A CN 202310058359 A CN202310058359 A CN 202310058359A CN 116476466 A CN116476466 A CN 116476466A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 239000011888 foil Substances 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 155
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 74
- 229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 36
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010955 niobium Substances 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 119
- 238000000137 annealing Methods 0.000 claims description 118
- 238000005096 rolling process Methods 0.000 claims description 86
- 238000004880 explosion Methods 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 20
- 238000005498 polishing Methods 0.000 claims description 18
- 230000003746 surface roughness Effects 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- 238000003466 welding Methods 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002360 explosive Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
- B21B27/02—Shape or construction of rolls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
- B22D27/045—Directionally solidified castings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geometry (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Abstract
The invention discloses a metal foil for hydrogen purification, which is of a sandwich structure, wherein palladium or palladium alloy is arranged on two sides of the sandwich structure, and metal niobium, vanadium or tantalum of 5B family is arranged in the middle layer. In addition, the invention also discloses a preparation method of the metal foil. The surface of the sandwich structure of the metal foil is palladium or palladium alloy, the interior is 5B metal niobium, vanadium or tantalum, and the palladium layer on the surface not only has better catalytic decomposition/recombination effect on hydrogen, but also has better hydrogen embrittlement resistance, plays a role in supporting the 5B metal in the middle layer, can obviously reduce the use amount of the metal palladium in the foil, and obviously reduces the cost of the material.
Description
Technical Field
The invention belongs to the technical field of metal material processing, and particularly relates to a metal foil for hydrogen purification and a preparation method thereof.
Background
The hydrogen energy has the advantages of various sources, zero terminal emission, wide application range and the like, has wide application prospect in the fields of energy, rail traffic, advanced manufacturing and the like, and has great significance in guaranteeing the energy safety of China and coping with global climate change by greatly developing the hydrogen energy. Hydrogen fuel cells are one of the most widely known hydrogen energy industry applications, have the advantages of high fuel energy conversion rate, low noise, zero emission and the like, and are widely paid attention to various governments and enterprises. However, hydrogen has the characteristics of low density, inflammability, explosiveness and the like, and has the defects of difficult hydrogen storage, large volume, difficult hydrogenation, high risk and the like in the links of transportation, distribution, hydrogenation and the like, so that the problems of hydrogen storage and transportation must be solved before the hydrogen fuel cell is fully popularized and applied.
The methanol reforming hydrogen fuel cell uses methanol as an energy carrier, generates hydrogen through chemical catalytic reforming and is used for the fuel cell, has the characteristics of small volume, low energy consumption, easily available raw materials, high safety and the like, solves the problems of hydrogen storage and transportation, gets rid of dependence on a hydrogenation station, and is one of the fuel cell technologies which are easiest to realize in China at present. The reformer is a key component of a hydrogen fuel cell for reforming methanol, and the gas after the reforming reaction of methanol contains a small amount of carbon monoxide, and the carbon monoxide is a serious poisoning agent of a catalyst, so that the performance of the cell is reduced or the service life of the cell is shortened.
The palladium membrane has strong selective permeability to hydrogen, simple equipment and continuous production, has the advantages of small size, silence and compactness, and is the only commercialized inorganic membrane for hydrogen separation and purification at present. At present, palladium membranes can be classified into self-supporting palladium membranes and composite palladium membranes according to the preparation process. The self-supporting palladium membrane is generally prepared by adopting a rolling method, and the method has simple technical process and is suitable for mass production of palladium membranes. The composite palladium membrane is prepared by coating a palladium metal membrane on the surface of a porous carrier (such as ceramic, stainless steel and the like), and compared with the self-supporting palladium membrane prepared by a rolling method, the hydrogen permeation rate of the composite palladium membrane is greatly improved. However, the physical properties of the porous carrier and the palladium membrane have larger difference, the structure is easy to be unstable under the condition of cold and hot circulation in the using process, and the porous stainless steel carrier is easy to diffuse with the palladium membrane in the long-term using process, so that the palladium membrane is invalid. Currently, the self-supporting palladium membrane prepared by the rolling method is the most commonly used hydrogen purification material in a methanol reforming hydrogen fuel cell.
The self-supporting palladium membrane is generally prepared by firstly preparing palladium or palladium alloy into an ingot by adopting a vacuum melting method, and the ingot is repeatedly cold-rolled for a plurality of times after high-temperature homogenization and combined with a necessary intermediate annealing mode until the ingot reaches the required thickness. At present, alloy brands commonly used for preparing palladium membranes include Pd, pdCu40, pdAG23, pdY8 and the like. However, with the continuous rising price of metallic palladium in recent years, the cost of palladium membranes prepared by direct casting and rolling is gradually increased, which greatly limits the application of palladium membranes in the field of hydrogen purification.
Therefore, the content of metal palladium in the palladium membrane (also called as palladium foil) is reduced, so that the use cost of the palladium membrane is further reduced, and the palladium membrane has great significance and wide application prospect.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a metal foil for hydrogen purification and a preparation method thereof, aiming at the defects of the prior art. The two sides of the sandwich structure of the metal foil are palladium or palladium alloy, the middle layer is 5B metal niobium, vanadium or tantalum, and the palladium layer on the surface not only has better catalytic decomposition/recombination function on hydrogen, but also has better hydrogen embrittlement resistance, plays a supporting role on the 5B metal in the middle layer, can obviously reduce the use amount of the metal palladium in the foil, and obviously reduces the cost of the material.
In order to solve the technical problems, the invention adopts the following technical scheme: the metal foil for hydrogen purification is characterized in that the metal foil is of a sandwich structure, palladium or palladium alloy is arranged on two sides of the sandwich structure, and the middle layer is made of 5B metal niobium, vanadium or tantalum.
In addition, the invention also provides a method for preparing the metal foil for hydrogen purification, which is characterized by comprising the following steps:
step one, preparing a palladium or palladium alloy plate: preparing a palladium cast ingot or a palladium alloy cast ingot by adopting a directional solidification method, and rolling the prepared cast ingot to a required size to correspondingly obtain a palladium plate or a palladium alloy plate;
step two, primary explosion compounding: adopting the palladium plate or the palladium alloy plate prepared in the first step as a clad plate, adopting a niobium plate, a vanadium plate or a tantalum plate as a substrate, polishing the surfaces of the clad plate and the substrate, and then stacking the substrates according to the clad plate, and performing explosion welding to obtain a primary explosion clad plate;
step three, secondary explosion compounding: flattening the primary explosion composite board in the second step, polishing the surface of the flattened primary explosion composite board, performing vacuum annealing, taking the annealed board as a substrate, placing the substrate on the ground to enable the palladium or palladium alloy surface to face downwards, taking the palladium board or palladium alloy board in the first step as a composite board, stacking the polished palladium board or palladium alloy board on the substrate, and performing explosion welding to obtain a secondary explosion composite board;
and step four, annealing the composite board: flattening the secondary explosion composite board in the third step, polishing the surface of the secondary explosion composite board subjected to flattening, and then carrying out vacuum annealing to obtain a composite board;
step five, rough rolling: rough rolling is carried out on the composite board in the step four by adopting a two-high mill, and a composite strip with the thickness of 0.8 mm-1.2 mm is obtained;
step six, middle rolling: performing intermediate rolling on the composite strip in the fifth step by adopting a four-high mill to obtain a composite strip with the thickness of 0.1-0.25 mm;
step seven, finish rolling: and D, performing finish rolling on the composite strip obtained in the step six by adopting a twenty-high rolling mill to obtain the metal foil with the thickness of 0.015-0.02 mm for hydrogen purification.
The method is characterized in that in the directional solidification process in the first step, the vacuum degree of the furnace body is not more than 1Pa, and the crucible pull-down speed is 50-200 mu m/s; the temperature of the melt is 100-300 ℃ higher than the melting point temperature of pure palladium when preparing palladium cast ingot, and the temperature is 10-30 min; the heat preservation temperature of the melt is 100-300 ℃ higher than the liquidus temperature of the alloy when preparing the palladium alloy cast ingot, the heat preservation time is 10-30 min, the palladium alloy cast ingot is subjected to homogenizing annealing treatment, the annealing temperature is 900-1100 ℃, and the annealing time is 2-4 h;
the method is characterized in that vacuum annealing treatment is carried out when the accumulated deformation amount in the rolling process reaches 70% in the first step, the temperature of the vacuum annealing treatment is 35-50% of the melting point temperature of pure palladium when the palladium plate is prepared, the annealing time is 0.5-2 h, the temperature of the vacuum annealing treatment when the palladium alloy plate is prepared is 35-50% of the solidus temperature of the alloy, and the annealing time is 0.5-2 h.
The method is characterized in that the ratio of the width to the length of the compound plate to the substrate in the second step is 1 (1.5-2), and the thickness ratio of the compound plate to the substrate is 1 (2-4).
The method is characterized in that the surface roughness of the polished compound plate and the polished substrate in the second step is not more than 20 mu m; and step three, the surface roughness of the polished primary explosion composite board is not more than 20 mu m.
The method is characterized in that the temperature of the vacuum annealing in the third step and the temperature of the vacuum annealing in the fourth step are 700-1000 ℃ and the time is 0.5-2 h.
The method is characterized in that the pass working rate in the rough rolling process in the step five is not lower than 20%, vacuum annealing is required when the accumulated deformation reaches 60% and after rough rolling is finished, the annealing temperature is 700-1000 ℃, and the annealing time is 0.5-2 h.
The method is characterized in that the pass processing rate in the rolling process in the step six is not lower than 15 percent, vacuum annealing is required when the accumulated deformation reaches 60 percent and after the intermediate rolling is finished, the annealing temperature is 700-1000 ℃, and the annealing time is 0.5-2 h;
the method is characterized in that the pass processing rate in the finish rolling process in the step seven is not more than 10%.
Compared with the prior art, the invention has the following advantages:
1. palladium and palladium alloys are very susceptible to gettering during smelting, so that alloy ingots prepared by gravity casting methods have relatively serious loose and air hole defects, which are difficult to completely eliminate during subsequent processing, and when foils are processed to very thin dimensions, the defects tend to develop into pinhole defects. Palladium and palladium alloys belong to the surface layer in the structure, and their surface quality determines the final service life of the material. According to the invention, the palladium and palladium alloy cast ingot is prepared by the directional solidification method, so that casting defects in the cast ingot can be effectively eliminated, and further, the surface quality of the foil is improved.
2. Compared with metal palladium, the 5B group metal has higher hydrogen solubility and better hydrogen diffusion performance and is cheaper, but the 5B group metal is easy to oxidize on one hand, so that the catalytic decomposition/recombination effect of the surface to hydrogen is reduced, on the other hand, the hydrogen embrittlement problem of the 5B group metal in the use process leads to lower lasting performance, and through the structural design of the invention, the palladium or palladium alloy layer on the surface not only has better catalytic decomposition/recombination effect to hydrogen, but also has better hydrogen embrittlement resistance and plays a supporting role to the 5B group metal of the middle layer. Therefore, the foil design of the sandwich structure can obviously reduce the use amount of metal palladium in the foil and obviously reduce the cost of materials.
3. Compared with a chemical method, the invention can greatly improve the bonding strength between the palladium composite layer and the matrix through explosive cladding and multipass rolling.
4. Because the explosive composite board base layer and the composite layer can have a false welding part, the false welding part can be eliminated by adopting a large pass processing rate in rough rolling, better combination between the composite layer and the matrix can be ensured, and better strip shape can be ensured in the foil forming process by adopting a large deformation amount and a small pass processing rate in finish rolling. Therefore, the method can better improve the product quality by setting the pass processing rate of the first and then the second pass processing rate.
The technical scheme of the invention is further described in detail through examples and attached drawings.
Drawings
FIG. 1 is a photograph of the microstructure of a cross section of a finished foil in example 1 of the present invention.
Detailed Description
Example 1
The metal foil for hydrogen purification in this embodiment is a sandwich structure, palladium alloy PdCu40 is disposed on two sides of the sandwich structure, and tantalum is disposed in the middle layer.
The preparation method of the metal foil for hydrogen purification in this embodiment comprises the following steps:
step one, preparing a palladium alloy plate: preparing a PdCu40 alloy cast ingot with the thickness of 20mm by adopting a directional solidification method, wherein in the directional solidification process, the vacuum degree of a furnace body is not more than 1Pa, the heat preservation temperature of a melt is 1530 ℃, the heat preservation time is 30min, the pull-down rate of a crucible is 200 mu m/s, the cast ingot is taken out after being cooled to room temperature after being solidified, and then the cast ingot is subjected to vacuum homogenization annealing treatment, the annealing temperature is 900 ℃, and the annealing time is 4h; rolling the annealed cast ingot to 1mm by adopting a two-roller mill to obtain a PdCu40 alloy plate, wherein vacuum annealing treatment is required when the deformation amount in the rolling process reaches 70%, the annealing temperature is 600 ℃, and the annealing time is 2 hours;
step two, primary explosion compounding: selecting a composite plate and a base plate with corresponding sizes according to the size of the finished composite plate, wherein the composite plate is a PdCu40 alloy plate in the first step, the base plate is a tantalum plate, the ratio of the width to the length of the composite plate to the base plate is 1:2, and the thickness of the base plate is 4mm; polishing the surfaces of the composite board and the base board until the surface roughness is no more than 20 mu m, then stacking the base board under the composite board according to the condition that the composite board is up, then paving explosive on the surface of the composite board, and igniting a detonator to detonate the explosive for explosion welding to obtain a primary explosion composite board;
step three, secondary explosion compounding: flattening the primary explosion composite board in the second step, polishing the surface of the primary explosion composite board subjected to flattening until the surface roughness is no more than 20 mu m, and then carrying out vacuum annealing at the annealing temperature of 1000 ℃ for 2 hours; taking the annealed primary explosion composite board as a base board, placing the base board on the ground, enabling the PdCu40 surface to face downwards, taking the PdCu40 alloy board in the other step one as a composite board, polishing the composite board, enabling the surface roughness of the composite board to be not more than 20 mu m, then stacking the composite board on the base board, paving explosive on the surface of the composite board, and igniting a detonator to detonate the explosive for explosion welding, so as to obtain a secondary explosion composite board;
and step four, annealing the composite board: flattening the secondary explosion composite board in the third step, polishing the surface of the secondary explosion composite board subjected to flattening treatment, wherein the surface roughness is not more than 20 mu m, and then carrying out vacuum annealing to obtain a composite board, wherein the annealing temperature is 1000 ℃ and the annealing time is 2 hours;
step five, rough rolling: rough rolling is carried out on the composite board in the step four by adopting a two-high mill to obtain a composite strip with the thickness of 1.2mm, the pass working rate in the rolling process is not lower than 20 percent, the accumulated deformation reaches 60 percent, and vacuum annealing is carried out after rough rolling is finished, wherein the specific rolling process is as follows: 6 mm- & gt 4.5 mm- & gt 3.3 mm- & gt 2.4 mm- & gt vacuum annealing- & gt 1.7 mm- & gt 1.2 mm- & gt vacuum annealing, wherein the annealing temperature is 1000 ℃ and the annealing time is 2 hours;
step six, middle rolling: and (3) performing intermediate rolling on the composite strip in the step five by adopting a four-high mill to obtain a composite strip with the thickness of 0.25mm, wherein the pass working rate in the rolling process is not lower than 15%, the accumulated deformation reaches 60%, and vacuum annealing is required after the intermediate rolling is finished, and the specific rolling process is as follows: 1.2 mm-1 mm-0.8 mm-0.65 mm-0.55 mm-0.45 mm-vacuum annealing-0.37 mm-0.3 mm-0.25 mm-vacuum annealing at 1000 deg.c for 2 hr;
step seven, finish rolling: finish rolling the composite strip in the step six by adopting a twenty-high rolling mill to obtain a metal foil with the thickness of 0.02mm for hydrogen purification, wherein the pass processing rate in the rolling process is not more than 10%; the specific rolling process is as follows: 0.25mm, 0.225mm, 0.205mm, 0.19mm, 0.172mm, 0.155mm, 0.14mm, 0.13mm, 0.12mm, 0.11mm, 0.1, 0.09mm, 0.081mm, 0.073mm, 0.066mm, 0.06mm, 0.054mm, 0.049mm, 0.045mm, 0.041mm, 0.037mm, 0.034mm, 0.031mm, 0.028mm, 0.026mm, 0.024mm, 0.022mm, 0.02mm.
The microstructure photograph of the section of the metal foil for hydrogen purification prepared in this example is shown in fig. 1, wherein palladium alloy PdCu40 is arranged on both sides of the figure, tantalum is arranged in the middle layer, the palladium copper alloy consumption of 66% can be saved by the structure, and the hydrogen permeation rate of the PdCu40 film is 2.8x10 under the temperature of 400 ℃ through test -8 mol·m -1 ·s -1 ·Pa -1/2 The hydrogen permeation rate of the PdCu40/Ta/PdCu40 composite film is 3.3X10 -8 mol·m -1 ·s -1 ·Pa -1/2 。
Example 2
This embodiment is the same as embodiment 1, except that: the heat preservation temperature of the melt in the first step is 1330 ℃, the heat preservation time is 10min, the annealing temperature of the vacuum homogenizing annealing treatment is 1100 ℃, and the annealing time is 2h; the temperature of the vacuum annealing treatment in the first step is 420 ℃, and the annealing time is 0.5h.
Example 3
This embodiment is the same as embodiment 1, except that: the heat preservation temperature of the melt in the first step is 1430 ℃, the heat preservation time is 20min, the annealing temperature of the vacuum homogenizing annealing treatment is 1000 ℃, and the annealing time is 3h; the temperature of the vacuum annealing treatment in the first step is 500 ℃, and the annealing time is 1h.
Example 4
The metal foil for hydrogen purification in this embodiment is a sandwich structure, palladium is disposed on two sides of the sandwich structure, and vanadium is disposed in the middle layer.
The preparation method of the metal foil for hydrogen purification in this embodiment comprises the following steps:
step one, preparing a palladium plate: preparing a pure palladium cast ingot with the thickness of 10mm by adopting a directional solidification method, wherein in the directional solidification process, the vacuum degree of a furnace body is not more than 1Pa, the heat preservation temperature of a melt is 1654 ℃, the heat preservation time is 10min, the pull-down rate of a crucible is 50 mu m/s, and the cast ingot is taken out after cooling to room temperature after solidification; rolling the annealed cast ingot to 1.5mm by adopting a two-roller mill to obtain a pure palladium plate, wherein vacuum annealing treatment is required when the deformation amount in the rolling process reaches 70%, the annealing temperature is 544 ℃, and the annealing time is 0.5h;
step two, primary explosion compounding: selecting a composite plate and a substrate with corresponding sizes according to the size of the finished composite plate, wherein the composite plate is a pure palladium plate in the first step, the substrate is a vanadium plate, the ratio of the width to the length of the composite plate to the substrate is 1:1.5, and the thickness of the substrate is 3mm; polishing the surfaces of the composite board and the base board until the surface roughness is no more than 20 mu m, then stacking the base board under the composite board according to the condition that the composite board is up, then paving explosive on the surface of the composite board, and igniting a detonator to detonate the explosive for explosion welding to obtain a primary explosion composite board;
step three, secondary explosion compounding: flattening the primary explosion composite board in the second step, polishing the surface of the primary explosion composite board subjected to flattening until the surface roughness is no more than 20 mu m, and then carrying out vacuum annealing at 700 ℃ for 0.5h; taking the annealed primary explosion composite board as a base board, placing the base board on the ground, wherein the palladium surface is downward, taking the pure palladium board in the other step I as a composite board, polishing the pure palladium board, enabling the surface roughness to be no more than 20 mu m, then stacking the pure palladium board on the base board, paving explosive on the surface of the composite board, and igniting a detonator to detonate the explosive for explosion welding to obtain a secondary explosion composite board;
and step four, annealing the composite board: flattening the secondary explosion composite board in the third step, polishing the surface of the secondary explosion composite board subjected to flattening treatment, wherein the surface roughness is not more than 20 mu m, and then carrying out vacuum annealing to obtain a composite board, wherein the annealing temperature is 700 ℃, and the annealing time is 0.5h;
step five, rough rolling: rough rolling is carried out on the composite board in the step four by adopting a two-high mill to obtain a composite strip with the thickness of 0.8mm, the pass working rate in the rolling process is not lower than 20 percent, the accumulated deformation reaches 60 percent, and vacuum annealing is carried out after rough rolling is finished, wherein the specific rolling process is as follows: 6mm, 4.2mm, 3mm, 2.2mm, vacuum annealing, 1.6mm, 1.2mm, 1mm
0.8 mm- & gt vacuum annealing, wherein the annealing temperature is 700 ℃ and the annealing time is 0.5h;
step six, middle rolling: and (3) performing intermediate rolling on the composite strip in the step five by adopting a four-high mill to obtain a composite strip with the thickness of 0.1mm, wherein the pass working rate in the rolling process is not lower than 15%, the accumulated deformation reaches 60%, and vacuum annealing is required after the intermediate rolling is finished, and the specific rolling process is as follows: 0.8 mm- & gt 0.6 mm- & gt 0.44 mm- & gt 0.31 mm- & gt vacuum annealing- & gt 0.24 mm- & gt 0.18 mm- & gt
0.14 mm-0.1 mm-vacuum annealing at 700 deg.c for 0.5 hr;
step seven, finish rolling: finish rolling the composite strip in the step six by adopting a twenty-high rolling mill to obtain a metal foil with the thickness of 0.015mm for hydrogen purification, wherein the pass processing rate in the rolling process is not more than 10%; the specific rolling process is as follows: 0.1mm, 0.09mm, 0.081mm, 0.073mm, 0.066mm, 0.06mm, 0.054mm, 0.049mm, 0.045mm, 0.041mm, 0.037, 0.034mm, 0.031mm, 0.028mm, 0.026mm, 0.024mm, 0.022mm, 0.02mm, 0.018mm, 0.017mm, 0.016mm, 0.015mm.
The microstructure photo of the section of the metal foil for hydrogen purification prepared in the embodiment is similar to that of FIG. 1, pure palladium is arranged on two sides, vanadium is arranged in the middle layer, the structure can save 50% of the pure palladium consumption, and the hydrogen permeation rate of the pure palladium membrane is 1.9X10 when tested at 400 DEG C -8 mol·m -1 ·s -1 ·Pa -1/2 The hydrogen permeation rate of the Pd/V/Pd composite membrane is 1.8X10 -8 mol·m -1 ·s -1 ·Pa -1/2 。
Example 5
This embodiment is the same as embodiment 4, except that: the temperature of the melt in the first step is 1854 ℃ and the temperature keeping time is 30min; the temperature of the vacuum annealing treatment in the first step is 777 ℃, and the annealing time is 2h.
Example 6
This embodiment is the same as embodiment 4, except that: the heat preservation temperature of the melt in the first step is 1754 ℃, the heat preservation time is 20min, the annealing temperature of the vacuum homogenizing annealing treatment is 900 ℃, and the annealing time is 4h; the temperature of the vacuum annealing treatment in the first step is 650 ℃, and the annealing time is 1.5h.
Example 7
The metal foil for hydrogen purification in this embodiment is a sandwich structure, two sides of the sandwich structure are palladium alloy PdAg23, and the middle layer is niobium.
The preparation method of the metal foil for hydrogen purification in this embodiment comprises the following steps:
step one, preparing a palladium alloy plate: preparing a PdAG23 alloy cast ingot with the thickness of 20mm by adopting a directional solidification method, wherein in the directional solidification process, the vacuum degree of a furnace body is not more than 1Pa, the heat preservation temperature of a melt is 1640 ℃, the heat preservation time is 20min, the pull-down rate of a crucible is 100 mu m/s, the cast ingot is taken out after being cooled to room temperature after being solidified, and then the cast ingot is subjected to vacuum homogenization annealing treatment, the annealing temperature is 1100 ℃, and the annealing time is 2h; rolling the annealed cast ingot to 1mm by adopting a two-roller mill to obtain a PdAG23 alloy plate, wherein vacuum annealing treatment is required when the deformation amount in the rolling process reaches 70%, the annealing temperature is 710 ℃, and the annealing time is 2 hours;
step two, primary explosion compounding: selecting a composite plate and a base plate with corresponding sizes according to the size of the finished composite plate, wherein the composite plate is a PdAG23 alloy plate in the first step, the base plate is a tantalum plate, the ratio of the width to the length of the composite plate to the base plate is 1:2, and the thickness of the base plate is 3mm; polishing the surfaces of the composite board and the base board until the surface roughness is no more than 20 mu m, then stacking the base board under the composite board according to the condition that the composite board is up, then paving explosive on the surface of the composite board, and igniting a detonator to detonate the explosive for explosion welding to obtain a primary explosion composite board;
step three, secondary explosion compounding: flattening the primary explosion composite board in the second step, polishing the surface of the primary explosion composite board subjected to flattening until the surface roughness is no more than 20 mu m, and then carrying out vacuum annealing at 900 ℃ for 1.5h; taking the annealed primary explosion composite board as a base board, placing the base board on the ground, enabling a PdCu40 surface to face downwards, taking the PdAG23 alloy board in the other step one as a composite board, polishing the composite board, enabling the surface roughness of the composite board to be not more than 20 mu m, then stacking the composite board on the base board, paving explosive on the surface of the composite board, and igniting a detonator to detonate the explosive for explosion welding, so as to obtain a secondary explosion composite board;
and step four, annealing the composite board: flattening the secondary explosion composite board in the third step, polishing the surface of the secondary explosion composite board subjected to flattening treatment, wherein the surface roughness is not more than 20 mu m, and then carrying out vacuum annealing to obtain a composite board, wherein the annealing temperature is 900 ℃ and the annealing time is 1.5h;
step five, rough rolling: rough rolling is carried out on the composite plate in the step four by adopting a two-high mill to obtain a composite strip with the thickness of 1mm, the pass working rate in the rolling process is not lower than 20 percent, the accumulated deformation reaches 60 percent, and vacuum annealing is carried out after rough rolling is finished, wherein the specific rolling process is as follows: 5 mm- & gt 3.5 mm- & gt 2.5 mm- & gt 1.8 mm- & gt vacuum annealing- & gt 1.3 mm- & gt 1 mm- & gt vacuum annealing, wherein the annealing temperature is 900 ℃ and the annealing time is 1.5h;
step six, middle rolling: and (3) performing intermediate rolling on the composite strip in the step five by adopting a four-high mill to obtain a composite strip with the thickness of 0.15mm, wherein the pass working rate in the rolling process is not lower than 15%, the accumulated deformation reaches 60%, and vacuum annealing is required after the intermediate rolling is finished, and the specific rolling process is as follows: 1 mm- & gt 0.75 mm- & gt 0.55 mm- & gt 0.4 mm- & gt vacuum annealing- & gt 0.3 mm- & gt 0.24 mm- & gt 0.18 mm- & gt 0.15 mm- & gt vacuum annealing, wherein the annealing temperature is 900 ℃ and the annealing time is 1.5h.
Step seven, finish rolling: finish rolling the composite strip in the step six by adopting a twenty-high rolling mill to obtain a metal foil with the thickness of 0.02mm for hydrogen purification, wherein the pass processing rate in the rolling process is not more than 10%; the specific rolling process is as follows: 0.15mm, 0.14mm, 0.13mm, 0.12mm, 0.11mm, 0.1mm, 0.09mm, 0.082mm, 0.075mm, 0.068mm, 0.062mm, 0.057mm, 0.052mm, 0.048mm, 0.044mm, 0.04, 0.036mm, 0.033mm, 0.03mm, 0.027mm, 0.025mm, 0.023mm, and 0.02mm.
The microstructure photo of the section of the metal foil for hydrogen purification prepared in the embodiment is similar to that of FIG. 1, pdAG23 is arranged on two sides, niobium is arranged in the middle layer, the structure can save 60% of pure palladium consumption, and the hydrogen permeation rate of the PdAG23 film is 3.8x10 at 400 ℃ through test -8 mol·m -1 ·s -1 ·Pa -1/2 The hydrogen permeation rate of the PdAG23/Nb/PdAG23 composite film is 4.2X10 -8 mol·m -1 ·s -1 ·Pa -1/2 。
Example 8
This embodiment is the same as embodiment 7, except that: the heat preservation temperature of the melt in the first step is 1560 ℃, the heat preservation time is 30min, the annealing temperature of the vacuum homogenizing annealing treatment is 900 ℃, and the annealing time is 4h; the temperature of the vacuum annealing treatment in the first step is 497 ℃ and the annealing time is 1.5h.
Example 9
This embodiment is the same as embodiment 7, except that: the heat preservation temperature of the melt in the first step is 1760 ℃, the heat preservation time is 10min, the annealing temperature of the vacuum homogenizing annealing treatment is 1000 ℃, and the annealing time is 3h; the temperature of the vacuum annealing treatment in the first step is 600 ℃, and the annealing time is 0.5h.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The metal foil for hydrogen purification is characterized in that the metal foil is of a sandwich structure, palladium or palladium alloy is arranged on two sides of the sandwich structure, and the middle layer is made of 5B metal niobium, vanadium or tantalum.
2. A method of preparing the hydrogen purging metal foil of claim 1, comprising the steps of:
step one, preparing a palladium or palladium alloy plate: preparing a palladium cast ingot or a palladium alloy cast ingot by adopting a directional solidification method, and rolling the prepared cast ingot to a required size to correspondingly obtain a palladium plate or a palladium alloy plate;
step two, primary explosion compounding: adopting the palladium plate or the palladium alloy plate prepared in the first step as a clad plate, adopting a niobium plate, a vanadium plate or a tantalum plate as a substrate, polishing the surfaces of the clad plate and the substrate, and then stacking the substrates according to the clad plate, and performing explosion welding to obtain a primary explosion clad plate;
step three, secondary explosion compounding: flattening the primary explosion composite board in the second step, polishing the surface of the flattened primary explosion composite board, performing vacuum annealing, taking the annealed board as a substrate, placing the substrate on the ground to enable the palladium or palladium alloy surface to face downwards, taking the palladium board or palladium alloy board in the first step as a composite board, stacking the polished palladium board or palladium alloy board on the substrate, and performing explosion welding to obtain a secondary explosion composite board;
and step four, annealing the composite board: flattening the secondary explosion composite board in the third step, polishing the surface of the secondary explosion composite board subjected to flattening, and then carrying out vacuum annealing to obtain a composite board;
step five, rough rolling: rough rolling is carried out on the composite board in the step four by adopting a two-high mill, and a composite strip with the thickness of 0.8 mm-1.2 mm is obtained;
step six, middle rolling: performing intermediate rolling on the composite strip in the fifth step by adopting a four-high mill to obtain a composite strip with the thickness of 0.1-0.25 mm;
step seven, finish rolling: and D, performing finish rolling on the composite strip obtained in the step six by adopting a twenty-high rolling mill to obtain the metal foil with the thickness of 0.015-0.02 mm for hydrogen purification.
3. The method according to claim 2, wherein in the directional solidification process in the first step, the vacuum degree of the furnace body is not more than 1Pa, and the crucible pull-down rate is 50 μm/s to 200 μm/s; the temperature of the melt is 100-300 ℃ higher than the melting point temperature of pure palladium when preparing palladium cast ingot, and the temperature is 10-30 min; the heat preservation temperature of the melt is 100-300 ℃ higher than the liquidus temperature of the alloy when the palladium alloy cast ingot is prepared, the heat preservation time is 10-30 min, the palladium alloy cast ingot is subjected to homogenizing annealing treatment, the annealing temperature is 900-1100 ℃, and the annealing time is 2-4 h.
4. The method according to claim 2, wherein the vacuum annealing treatment is performed when the cumulative deformation amount in the rolling process reaches 70% in the first step, the temperature of the vacuum annealing treatment in the preparation of the palladium sheet is 35-50% of the melting point temperature of pure palladium, the annealing time is 0.5-2 h, the temperature of the vacuum annealing treatment in the preparation of the palladium alloy sheet is 35-50% of the solidus temperature of the alloy, and the annealing time is 0.5-2 h.
5. The method of claim 2, wherein in the second step, the ratio of the width to the length of the composite plate to the substrate is 1 (1.5-2), and the ratio of the thickness of the composite plate to the substrate is 1 (2-4).
6. The method according to claim 2, wherein the surface roughness of the polished composite plate and the polished substrate in the second step is not more than 20 μm; and step three, the surface roughness of the polished primary explosion composite board is not more than 20 mu m.
7. The method according to claim 2, wherein the temperature of the vacuum annealing in the third step and the vacuum annealing in the fourth step are each 700 ℃ to 1000 ℃ for 0.5h to 2h.
8. The method according to claim 2, wherein the pass reduction ratio in the rough rolling process in the fifth step is not lower than 20%, vacuum annealing is performed when the accumulated deformation reaches 60% and after the rough rolling is finished, the annealing temperature is 700 ℃ to 1000 ℃, and the annealing time is 0.5h to 2h.
9. The method according to claim 2, wherein the pass reduction ratio in the rolling process in the step six is not lower than 15%, vacuum annealing is performed when the accumulated deformation reaches 60% and after the intermediate rolling is finished, the annealing temperature is 700 ℃ to 1000 ℃, and the annealing time is 0.5h to 2h.
10. The method according to claim 2, wherein the pass reduction ratio during finish rolling in step seven is not more than 10%.
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