A kind of V-Cu systems monotectic type hydrogen separation alloy and its processing method
Technical field
The present invention relates to a kind of hydrogen separation alloy and its processing method.
Background technology
In 21 century, principal element of the energy problem with environmental problem into restriction industrial development, and Hydrogen Energy has reserves
Greatly, many advantages, such as calorific value is high gets most of the attention in new energy field.Due to semiconductor, space flight and aviation, fuel cell, high-energy fuel
Deng requirement of the numerous areas to hydrogen purity at least more than 99.999%, thus there is an urgent need to find it is a kind of efficiently, it is cheap, can follow
The method of ring obtains High Purity Hydrogen.High Purity Hydrogen is mainly obtained by the way that obtained low pure hydrogen is purified and purified at present, and film point
It is current maximally effective technology for hydrogen purification from technology, wherein filter hydrogen palladium film is used widely in hydrogen purification field.
But palladium resource is not only expensive, be not suitable for heavy industrialization application, and with other alloy infusibilities, developable alloy
Be it is less because pure V (vanadium) have it is higher than palladium ooze hydrogen performance, therefore V alloy turn into hydrogen separation alloy Main way it
One.
According to the chemical characteristic and physical characteristic for oozing hydrogen alloy, can be greatly improved by the thickness for reducing hydrogen separation alloy
The alloy oozes hydrogen flowrate.It is mainly logical to the progress of as cast condition V base hydrogen separation alloy on V base hydrogen separation alloys preparation method at present
Wire cutting, the alloy finite thickness that this method obtains, and in view of the characteristics of V based alloy temperature-room type plasticity poor processabilities, have
The method that person is combined using hot rolling with cold rolling obtains 0.2mm sheet material, it is found that the process is not only consumed greatly to foundry alloy, and
And manufacturing procedure is more, process is complicated.As demand of the industrialized production for High Purity Hydrogen increasingly increases, prepare on a large scale sheet material into
For the important point of penetration of hydrogen separation alloy industrial applications.
Therefore, a kind of vanadium base hydrogen separation alloy that not only there is high osmosis but also there can be high-ductility is found, is art technology
The problem of personnel's urgent need to resolve.
The content of the invention
The present invention is that the method for obtaining seperation film to solve existing vanadium base hydrogen separation alloy to cut ingot casting has film
Piece minimum thickness is bigger than normal and the problem of waste of raw materials.
A kind of V-Cu systems monotectic type hydrogen separation alloy, the hydrogen separation alloy include V, Cu, and can be with V-arrangement Cheng Gu
The solute metal element of solution;On the microstructure of hydrogen separation alloy, V is bcc-V (body-centred cubic vanadium), Cu fcc-
Cu (face-centred cubic copper);The atomic percent of the V is 56.5%-90%, and the atomic percent of the Cu is 10%-
40%, described can be 0%-9% with the atomic percent of V-arrangement into the solute metal element of solid solution.
Preferably, the atomic percent of the V is 56.5%-81%, and the atomic percent of the Cu is 10%-40%,
Described can be 3.5%-9% with the atomic percent of V-arrangement into the solute metal element of solid solution.
Preferably, the solute metal element of described formation solid solution includes one kind in Cr, Fe, Al, Co, Ni, Mo, Pd
It is or a variety of.
A kind of processing method of V-Cu systems monotectic type hydrogen separation alloy, comprises the following steps:
Step 1 and accurate weighing pure V and pure Cu, or the solute element metal of the pure V of accurate weighing, pure Cu and solid solution,
Then melting is carried out to the raw material of proportioning;
Step 2, cold rolling:Carry out room temperature rolling to melted as cast condition master alloy ingot, reduction in pass 0.1-0.25mm,
Total deformation on thickness is 86-99%;
Step 3, Technology for Heating Processing:To make alloy meet the needs of good combination property, stone is passed through to the sheet material after rolling
It is put into after the English seal of tube in heat-treatment furnace, heat treatment temperature control is at 650-1000 DEG C, heat treatment time 1-168h;
Step 4, to after heat treatment plate surface carry out grinding and buffing, then sheet coupon tow sides respectively with
The mode of sputter coating plates the thick palladium films of 150nm, and the hydrogen separation alloy diaphragm needed for experiment is made.
Preferably, the heat treatment temperature described in step 3 is depending on the property of hydrogen separation alloy and atomic percent:
(1) when hydrogen separation alloy is V-Cu bianry alloys, heat treatment temperature is 650-800 DEG C;Cu atomic percent
For 40% when, heat treatment temperature be 650 DEG C;When Cu atomic percent is 10%, heat treatment temperature is 800 DEG C;And Cu original
Corresponding heat treatment temperature is lower when sub- percentage is higher.
(2) when hydrogen separation alloy is ternary alloy three-partalloy, heat treatment temperature is 650-1000 DEG C, will be removed in hydrogen separation alloy
V, the metallic element beyond two kinds of elements of Cu is referred to as third element;
When third element metal is Al, heat treatment temperature is 650-680 DEG C, and Cu atomic percent is higher, Al
Corresponding heat treatment temperature is lower when atomic percent is higher;
When third element metal is Fe, Co, Ni or Pd, heat treatment temperature is 650-850 DEG C, and Cu atomic percent
Corresponding heat treatment temperature is lower when higher, Fe, Co, Ni or Pd atomic percent is lower;
When third element metal is Cr or Mo, heat treatment temperature be 800-1000 DEG C, and Cu atomic percent it is higher,
Cr or Mo atomic percent when lower corresponding heat treatment temperature it is lower.
(3) when hydrogen separation alloy is quaternary and above alloy, heat treatment temperature is 650-1000 DEG C, by hydrogen separation alloy
The middle metallic element removed beyond two kinds of elements of V, Cu is referred to as other constituent elements;
When other constituent elements include Cr, Mo and not containing Al, Fe, Co, Ni or Pd, heat treatment temperature 800-1000
DEG C, and corresponding heat treatment temperature is lower when Cu atomic percent is higher, Cr, Mo atomic percent are lower;
When other constituent elements include Fe, Co, Ni and/or Pd and do not contain Al, heat treatment temperature is 650-850 DEG C, and Cu
Atomic percent it is higher, corresponding heat treatment temperature is lower when atomic percent of Fe, Co, Ni and/or Pd is lower;
When other constituent elements include Al, heat treatment temperature is 650-680 DEG C, and Cu atomic percent is higher, Al original
Corresponding heat treatment temperature is lower when sub- percentage is higher.
Preferably, the heat treatment time described in step 3 is 120-168h.
The present invention has the following effects that:
Alloy of the present invention or the alloy manufactured using the inventive method are that there is one kind high-ductility and Gao Qing to ooze
The V-Cu monotectic type hydrogen separation alloys of permeability, the advantage is that the content that can reduce V in matrix alloy, while change bcc-V
The lattice structure of solid solution, so as to reduce the hydrogen solubility of alloy, improve the hydrogen embrittlement of alloy.
And the present invention can carry on the basis of the high hydrogen permeability of the V base hydrogen separation alloys before keeping adding Cu
The plastic deformation ability of high alloy material;Alloy of the present invention can be applicable rolling mill practice, can be by hydrogen separation alloy film
Piece is accomplished producing the filter hydrogen metal film (energy that thickness is smaller compared with tradition cuts casting ingot method in the case of ensureing to ooze Hydrogen Energy power
Enough it is fabricated to 0.1mm sheet material), the diaphragm of required diameter is then made using wire cutting, can greatly save resource.
Using cut casting ingot method can obtain 7-8 pieces filter hydrogen metal film V based alloys, cutting casting ingot method can produce compared with
More waste of material;And alloy of the present invention or using the inventive method manufacture alloy can roll, then to plate
Material is cut, and will not cause the excessive waste of material;Compared with cutting casting ingot method, the V-Cu bases hydrogen point based on same volume
From alloy cast ingot, 30-40 pieces filter hydrogen metal film can be produced by rolling cutting using the present invention.
Meanwhile on the premise of permeance property change less, the V-Cu bases filter hydrogen metal film obtained is cut in present invention rolling
Cost of alloy, processing cost are all lower, and possess more preferable hydrogen embrittlement, and industrial applications have a extensive future.
Brief description of the drawings
Fig. 1 is the master alloy ingot pictorial diagram that embodiment 1 prepares V-Cu base hydrogen separation alloys;
Fig. 2 is the as-cast microstructure figure of master alloy ingot prepared by embodiment 1;
Fig. 3 is the rolled plate pictorial diagram that embodiment 1 prepares V-Cu base hydrogen separation alloys;
Fig. 4 V-Cu hydrogen separation alloy films ooze hydrogen result figure;
Fig. 5 is (V-10Fe)90Cu10Hydrogen separation alloy oozes hydrogen flowrate schematic diagram;
Fig. 6 (V-5Cr)90Cu10Hydrogen separation alloy oozes hydrogen flowrate schematic diagram.
Embodiment
Embodiment one:
A kind of V-Cu systems monotectic type hydrogen separation alloy, the hydrogen separation alloy include V, Cu, and can be with V-arrangement Cheng Gu
The solute metal element of solution;On the microstructure of hydrogen separation alloy, V is bcc-V (body-centred cubic vanadium), Cu fcc-
Cu (face-centred cubic copper);The atomic percent of the V is 56.5%-90%, and the atomic percent of the Cu is 10%-
40%, described can be 0%-9% with the atomic percent of V-arrangement into the solute metal element of solid solution.
It is to reduce the hydrogen solubility in hydrogen separation alloy, and raising modeling that Cu additions are set into 10-40% (At.%)
The reason of deformation ability;If Cu additions less than 10% (At.%), just can not realize the energy of alloy cold deformation at room temperature
Power;If Cu additions will cause the hydrogen separation alloy hydrogen penetrating quality to be decreased obviously, not reach pre- more than 40% (At.%)
The effect of phase.
Embodiment two:
The atomic percent of V described in present embodiment is 56.5%-81%, and the atomic percent of the Cu is 10%-
40%, described can be 3.5%-9% with the atomic percent of V-arrangement into the solute metal element of solid solution.
It is to reduce the hydrogen solubility in hydrogen separation alloy, and raising modeling that Cu additions are set into 10-40% (At.%)
The reason of deformation ability;If Cu additions less than 10% (At.%), just can not realize the energy of alloy cold deformation at room temperature
Power;If Cu additions will cause the hydrogen separation alloy hydrogen penetrating quality to be decreased obviously, not reach pre- more than 40% (At.%)
The effect of phase.
The atomic percent for reducing V simultaneously is 56.5%-81%, and increase forms the atom of the solute metal element of solid solution
Percentage is 3.5%-9%, can so adjust the lattice parameter of V alloy, reduces hydrogen dissolving, resists so as to improve hydrogen separation alloy
Hydrogen brittleness.The solute metal element of addition can be with V-arrangement into vanadium base solid solution, microstructure and bond energy that so could be to V, crystalline substance
Lattice parameter is produced to oozing hydrogen performance favorable influence.But be not all metal of addition can, if the metal of addition
It can not can not only increase the combination property of alloy with V-arrangement into solid solution, but also can have a strong impact on alloy oozes hydrogen performance.
Other compositions and parameter are identical with embodiment one.
Embodiment three:
The solute metal element of formation solid solution described in present embodiment is included in Cr, Fe, Al, Co, Ni, Mo, Pd
It is one or more.
Other compositions and parameter are identical with embodiment one or two.
The metallic atoms such as Cr, Fe, Al, Co, Ni, Mo, Pd and V-arrangement, could be to V microstructures and key into vanadium base solid solution
Energy, lattice parameter are produced to oozing hydrogen performance favorable influence.But be not all metal of addition can, the metal of addition
If can not be with V-arrangement into solid solution, can not only increase alloy oozes hydrogen performance, but also can have a strong impact on alloy oozes hydrogen
Energy.Can the one or more in Cr, Fe, Al, Co, Ni, Mo, Pd with V-arrangement into solid solution be needed by multiple when mixing
Test and the microstructure of tested alloys is tested and observed and analyzed, while also the hydrogen performance of oozing of alloy is carried out
Determine and judge, empirically can not can just illustrate the metal that addition is can serve as with the metal of V-arrangement into solid solution.But
Need to summarize and analyze based on the result to all hydrogen permeability tests, and combine to be added with and ooze hydrogen performance beneficial to hydrogen separation alloy
Metal after alloy microstructure result of the test be inferred to can with V-arrangement into solid solution metal just can be used as solute member
Element.Moreover, favorable influence is caused to hydrogen separation alloy for addition whether can be merged with the metal of V-arrangement into solid solution
And need to be tested by test of many times and to the microstructure of tested alloys and observed and analyzed;Whole process need through
Tested after many times, test number (TN) when being mixed in particular for a variety of solute elements is more.Can be by having although experiment is
Limit time is realized, but the workload tested is very big, and the time of consuming is also very long, so one in Cr, Fe, Al, Co, Ni, Mo, Pd
Kind or a variety of selections addition can not be estimated by common knowledge.
And the atomic percent for forming the metal of solid solution is that 3.5%-9% is also that just can determine that by test of many times
Scope.By verification experimental verification, once the atomic percent for forming the solute metal of solid solution is more than 9%, it can not only increase conjunction
The combination property of gold, but also can have a strong impact on alloy oozes hydrogen performance.And the atomic percent for forming the metal of solid solution is small
It is more or less the same in 3.5% with the hydrogen performance of oozing of the hydrogen separation alloy of V-Cu binary, only forms the atom hundred of the metal of solid solution
When dividing than being 3.5%-9%, ooze hydrogen performance and be greatly improved or lifted.
Embodiment four:
A kind of processing method of V-Cu systems monotectic type hydrogen separation alloy film, comprises the following steps:
Step 1 and accurate weighing pure V and pure Cu, or the solute element metal of the pure V of accurate weighing, pure Cu and solid solution,
Then melting is carried out to the raw material of proportioning;
Step 2, cold rolling:Carry out room temperature rolling to melted as cast condition master alloy ingot, reduction in pass 0.1-0.25mm,
Total deformation on thickness is 86-99%;
Step 3, Technology for Heating Processing:To make alloy meet the needs of good combination property, stone is passed through to the sheet material after rolling
It is put into after the English seal of tube in heat-treatment furnace, heat treatment temperature control is at 650-1000 DEG C, heat treatment time 1-168h;
Step 4, to after heat treatment plate surface carry out grinding and buffing, then sheet coupon tow sides respectively with
The mode of magnetron sputtering plating plates the thick palladium films of 150nm, the hydrogen separation alloy diaphragm needed for experiment is made, you can ooze to carry out hydrogen
Experiment thoroughly.
Embodiment five:
Heat treatment temperature in present embodiment described in step 3 according to the property and atomic percent of hydrogen separation alloy and
It is fixed:
(1) when hydrogen separation alloy is V-Cu bianry alloys, heat treatment temperature is 650-800 DEG C;Cu atomic percent
For 40% when, heat treatment temperature be 650 DEG C;When Cu atomic percent is 10%, heat treatment temperature is 800 DEG C;And Cu original
Corresponding heat treatment temperature is lower when sub- percentage is higher.
(2) when hydrogen separation alloy is ternary alloy three-partalloy, heat treatment temperature is 650-1000 DEG C, will be removed in hydrogen separation alloy
V, the metallic element beyond two kinds of elements of Cu is referred to as third element;
When third element metal is Al, heat treatment temperature is 650-680 DEG C, and Cu atomic percent is higher, Al
Corresponding heat treatment temperature is lower when atomic percent is higher;
When third element metal is Fe, Co, Ni or Pd, heat treatment temperature is 650-850 DEG C, and Cu atomic percent
Corresponding heat treatment temperature is lower when higher, Fe, Co, Ni or Pd atomic percent is lower;
When third element metal is Cr or Mo, heat treatment temperature be 800-1000 DEG C, and Cu atomic percent it is higher,
Cr or Mo atomic percent when lower corresponding heat treatment temperature it is lower.
(3) when hydrogen separation alloy is quaternary and above alloy, heat treatment temperature is 650-1000 DEG C, by hydrogen separation alloy
The middle metallic element removed beyond two kinds of elements of V, Cu is referred to as other constituent elements;
(Al, Fe, Co, Ni or Pd are not contained when other constituent elements include Cr, Mo), heat treatment temperature is 800-1000 DEG C,
And corresponding heat treatment temperature is lower when Cu atomic percent is higher, Cr, Mo atomic percent are lower;
When other constituent elements include Fe, Co, Ni and/or Pd and do not contain Al, heat treatment temperature is 650-850 DEG C, and Cu
Atomic percent it is higher, corresponding heat treatment temperature is lower when atomic percent of Fe, Co, Ni and/or Pd is lower;
When other constituent elements include Al, heat treatment temperature is 650-680 DEG C, and Cu atomic percent is higher, Al original
Corresponding heat treatment temperature is lower when sub- percentage is higher.
Other steps and parameter are identical with embodiment four.
Embodiment six:
Heat treatment time in present embodiment described in step 3 is 120-168h.
Other steps and parameter are identical with embodiment four or five.
Actual heat treatment time be by experiment grope come.Different heat treatment is had for the composition of different-alloy
Time, the heat treatment time for different-alloy composition are that hydrogen separation alloy has the most rational heat treatment for well oozing hydrogen performance
Time, after it exceedes certain heat treatment time, hydrogen separation alloy oozes hydrogen performance and will not be significantly improved or even can decline.
Embodiment
Embodiment 1
Scheme according to embodiment four prepare V atomic percents be 70%, Cu atomic percents be 30% it is inclined
Crystal formation hydrogen separation alloy.Calculate to obtain V and Cu mass percent according to atomic percent, as shown in table 1.
The V of table 170Cu30Alloying ingredient table
Components Name |
Atomic weight |
Atomic percent (%) |
Mass percent (%) |
V vanadium |
50.9415 |
70 |
65.163 |
Cu copper |
63.546 |
30 |
34.837 |
Step 1, prepare as cast condition master alloy ingot:
Pure V needed for molten alloy ingot and pure Cu are cleaned up, and the metal raw needed for each composition alloy of accurate weighing
Material, the raw material prepared are put into non-consumable arc-melting furnace carry out melting afterwards, obtain foundry alloy as shown in Figure 1
Ingot, corresponding as-cast structure are as shown in Figure 2;
Step 2, cold rolling:
Sheet material (0.1mm sheet material) as shown in Figure 3 is made with the drafts of 0.2mm/ passages using milling train;
Step 3, Technology for Heating Processing:
By sheet material by being put into after the quartzy seal of tube in heat-treatment furnace, 168h is heat-treated at 700 DEG C;
Step 4, alloy is taken out, make diaphragm:
Heat treatment takes out alloy after terminating from body of heater, and the hydrogen separation alloy diaphragm needed for experiment is made using wire cutting.
Obtained V70Cu30The hydrogen penetrating quality of monotectic type hydrogen separation alloy diaphragm and the relation of temperature are as shown in figure 4, Fig. 4
Middle ordinate be hydrogen infiltration coefficient (under unit upstream and downstream pressure difference, in the unit interval by mole of the hydrogen of unit thickness diaphragm
Amount), unit is mol H2m-1s-1Pa-0.5, the 1E-6 expressions 1 × 10 of ordinate scale-6;Abscissa represents temperature or 1000/
Temperature, the abscissa of top is temperature in Fig. 4, and unit is K (Kelvin);The abscissa of lower section is 1000/T in Fig. 4, and T is represented
Kelvin degree, unit K.
Embodiment 2
With reference to the scheme of embodiment 1, heat treatment temperature uses 800 DEG C, and it is 90%, Cu atoms hundred to prepare V atomic percents
Divide than the V for 10%90Cu10The hydrogen penetrating quality of monotectic type hydrogen separation alloy diaphragm and the relation of temperature are as shown in Figure 4.
Embodiment 3
With reference to the scheme of embodiment 1, heat treatment temperature uses 650 DEG C, and it is 60%, Cu atoms hundred to prepare V atomic percents
Divide than the V for 40%60Cu40The hydrogen penetrating quality of monotectic type hydrogen separation alloy diaphragm and the relation of temperature are as shown in Figure 4.
Embodiment 4
With reference to the scheme of embodiment 1, heat treatment temperature uses 800 DEG C, and it is 81%, Cu atoms hundred to prepare V atomic percents
Divide (V-10Fe) that ratio is 9% for 10%, Fe atomic percents90Cu10Monotectic type hydrogen separation alloy diaphragm, thickness 0.4mm.
Hydrogen production device is oozed using autonomous Design, different pressure is given at hydrogen separation alloy both ends, observes and records hydrogen separation alloy and ooze
Hydrogen data, as a result as shown in figure 5, being with unit interval, the transmission hydrogen of unit area diaphragm in ordinate in 5 in figure in 673K
What gas mole represented oozes hydrogen flowrate, and unit is mol H2m-2s-1;Pu represents end pressure on hydrogen separation alloy, and Pd represents hydrogen separation
End pressure under alloy;Abscissa is time t, unit min.
Embodiment 5
With reference to the scheme of embodiment 1, heat treatment temperature uses 800 DEG C, and it is 56.5%, Cu atoms to prepare V atomic percents
(V-5Cr) that percentage is 40%, Cr atomic percents are 3.5%90Cu10Monotectic type hydrogen separation alloy diaphragm, diaphragm thickness are
0.1mm.Hydrogen production device is oozed using autonomous Design, different pressure is given at hydrogen separation alloy both ends, observes and records hydrogen separation
Alloy oozes hydrogen data, as a result as shown in Figure 6.