CN117773099A - Porous titanium alloy substrate prepared based on spherical titanium alloy powder and preparation method thereof - Google Patents
Porous titanium alloy substrate prepared based on spherical titanium alloy powder and preparation method thereof Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 111
- 239000000843 powder Substances 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 32
- 239000001099 ammonium carbonate Substances 0.000 claims description 32
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 30
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 30
- 239000001509 sodium citrate Substances 0.000 claims description 25
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 25
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 24
- 239000000395 magnesium oxide Substances 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 20
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 18
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 210000001161 mammalian embryo Anatomy 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 229940105963 yttrium fluoride Drugs 0.000 claims description 2
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 32
- 238000005245 sintering Methods 0.000 abstract description 22
- 239000007789 gas Substances 0.000 abstract description 15
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- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000010146 3D printing Methods 0.000 abstract description 4
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
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- 239000000463 material Substances 0.000 description 6
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- 150000002431 hydrogen Chemical class 0.000 description 4
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- 239000000523 sample Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
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- 229910000048 titanium hydride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder and a preparation method thereof, wherein the raw materials of the porous titanium alloy substrate comprise 90-96 parts of spherical titanium alloy powder, 3-8 parts of pore-forming agent, 1-3 parts of metal oxide and 1-2 parts of metal fluoride. According to the invention, after the titanium alloy powder is mixed with the pore-forming agent, the metal oxide and the metal fluoride for pressing treatment, a specific sintering process is matched, and the prepared porous titanium alloy substrate has excellent acid and alkali resistance and corrosion resistance, excellent mechanical property and good conductivity, and also has rich and uniform pores. Particularly, when the porous material is used as a gas diffusion layer, excellent heat conduction and electric conductivity can be provided, and sufficient pores can also provide sufficient transmission channels for hydrogen, oxygen and the like while excellent mechanical properties are maintained. The titanium alloy powder used in the invention is coarse waste powder for 3D printing, has low production cost, simple preparation process and high safety, and can realize quantitative production.
Description
Technical Field
The invention relates to the technical field of porous titanium alloy materials, in particular to a porous titanium alloy substrate prepared based on spherical titanium alloy powder and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are key carriers for realizing conversion and utilization of hydrogen energy to electric energy, have the advantages of low working temperature, no pollution, no corrosion, high specific power, quick start and the like, and have become one of hot spots for research in the energy field. The gas diffusion layer, which is the core component thereof, is structurally and directly connected with the fuel cell plate and the catalytic layer, serves to transfer water, hydrogen, oxygen, and catalyst, and provides a mechanical role for these materials. It not only plays a role in transporting the reaction medium, but also continuously conducts heat and electricity. Therefore, the gas diffusion layer material is required to have excellent electrical conductivity, excellent mechanical strength, and sufficient gas transmission channels, and to have corrosion resistance, acid resistance, and the like, so that it can stably operate under the conditions of strong acidity, strong potential of the fuel cell.
Titanium and titanium alloys have low density, high specific strength, and excellent corrosion resistance in an acidic environment, and are often used as a material for gas diffusion layers. And corrosion products generated by titanium and titanium alloy in the long-term service running process have weak toxicity to the proton exchange membrane and the catalyst, thereby being beneficial to improving the running stability and durability of the battery. In the prior art, titanium powder or titanium hydride powder is often used as a preparation raw material, and because the hardness of the titanium powder is relatively soft, the titanium substrate is easier to produce by punching, and the titanium powder or the hydrogenation dehydrogenation titanium powder is often used as the raw material. However, the problems of uneven aperture, easy warping and cracking of the substrate during punching, poor surface flatness and the like still exist during punching production. However, the titanium alloy raw material has higher hardness, so that the problems are more likely to occur during the press firing.
Therefore, how to produce porous titanium substrates with abundant pores, uniform pore diameter, good conductivity, better mechanical strength and high surface flatness, and especially to produce harder titanium alloy powder into porous titanium alloy substrates is still a great research focus.
Disclosure of Invention
In view of the above problems, the present invention provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, which has excellent acid and alkali resistance and corrosion resistance, uniform pore diameter, good electrical conductivity, and can provide excellent electrical and thermal conductivity when used as a gas diffusion layer; the surface flatness is high, and the contact performance is good when the membrane electrode assembly is carried out, so that the problems of increasing contact resistance and the like are avoided. In addition, the titanium alloy powder used in the invention is waste powder for 3D printing, so that the resource utilization can be carried out, and the cost is effectively saved.
The invention provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, which comprises, by weight, 90-96 parts of spherical titanium alloy powder, 3-8 parts of pore-forming agent, 1-3 parts of metal oxide and 1-2 parts of metal fluoride.
Preferably, the porous titanium alloy substrate has a porosity of 30-50%, an average gas pore diameter of 20-50um and a thickness of 0.5-5mm.
Preferably, the average particle size of the spherical titanium alloy powder is 45-150 mu m, and the purity is more than or equal to 99%.
Preferably, the spherical titanium alloy powder is one or a mixture of more of TC4, TC6, TA7, TA15, TC11 and TC 18.
The titanium alloy powder used in the invention is coarse waste powder of the titanium alloy powder for 3D printing, thereby realizing effective utilization of titanium alloy resources and greatly saving cost.
Preferably, the pore-forming agent is one or more of ammonium bicarbonate, ammonium carbonate, citric acid, sodium citrate, ammonium citrate, urea, sodium carbonate, magnesium carbonate, potassium carbonate, stearic acid and sodium stearate.
Preferably, the pore-forming agent is ammonium bicarbonate, sodium citrate, and sodium stearate. More preferably, the mass ratio of the ammonium bicarbonate to the sodium citrate to the sodium stearate is 1:0.3-0.5:0.1-0.3.
More preferably, the ammonium bicarbonate, sodium citrate and sodium stearate are mixed and ball milled for 1-2 hours.
In the manufacture of porous titanium alloy substrates, the pores formed in the substrate originate mainly from the pores left after the decomposition of the pore-forming agent or from the micro-pore gaps generated by the shrinkage and accumulation of the titanium alloy material during the sintering of the material. The ammonium bicarbonate, sodium citrate and sodium stearate have the advantages of easy volatilization, good chemical stability and the like, and the raw materials are wide in source and low in cost. According to the invention, ammonium bicarbonate, sodium citrate and sodium stearate with the mass ratio of 1:0.3-0.5:0.1-0.3 are used as pore-forming agents, so that uniform pores can be formed in the titanium alloy substrate. Ammonium bicarbonate has good deformability, is easy to roll, has poor fluidity, is easy to distribute unevenly in a raw material system, and for ammonium bicarbonate particles with larger particle size, mechanical stirring is generally adopted to break up part of ammonium bicarbonate particles to form irregular ammonium bicarbonate particles with sharp corners, but is difficult to uniformly disperse in alloy powder; and the ammonium bicarbonate has the characteristics of water absorption and deliquescence, and ammonium bicarbonate with small particle size is easy to agglomerate at room temperature, so that the dispersion uniformity of the ammonium bicarbonate is more influenced. Therefore, the uniform dispersion of the pore-forming agent in the material system can be enhanced by simultaneously adding sodium citrate and sodium stearate for coaction, so that the prepared titanium alloy substrate has uniform pore distribution. And the inventors found that under this condition, the pore diameter formed is a through-hole structure, and particularly when used as a gas diffusion layer, it can provide a sufficient transport path for hydrogen, oxygen, and the like.
Preferably, the metal oxide is one or a mixture of magnesium oxide, zinc oxide and yttrium oxide.
Preferably, the average particle size of the magnesium oxide is less than or equal to 0.5 mu m, and the purity is more than or equal to 99 percent. More preferably, the magnesium oxide has an average particle diameter of 50 to 200nm.
Preferably, the metal fluoride is one or more of magnesium fluoride, calcium fluoride and yttrium fluoride.
More preferably, the metal fluoride is magnesium fluoride. In the invention, the particle size of the magnesium fluoride is preferably 200-400 meshes, and the purity is more than or equal to 98%.
According to the invention, the metal oxide and the metal fluoride are added, the average grain diameter of the magnesium oxide is less than or equal to 0.5 mu m, the grain diameter of the magnesium fluoride is 200-400 meshes, and the magnesium fluoride and the titanium alloy material can form a solid solution phase or a eutectic, so that the sintering temperature can be effectively reduced, the experiment cost is reduced, and the prepared titanium alloy substrate has uniform pore diameter and higher porosity.
The addition of magnesium fluoride can effectively reduce sintering temperature, improve sintering density, greatly improve sintering degree, and is easy to remove by acid washing, but has high price. By matching with the magnesium oxide, the cost can be reduced, and meanwhile, the magnesium oxide with small particle size can be better dispersed in the system, so that the sintering temperature is more uniform. However, magnesium oxide has high reactivity to titanium alloy systems and is extremely liable to introduce impurities, so that the amount of magnesium oxide used cannot be too large. The total usage amount of the metal oxide and the metal fluoride cannot be too high, or more impurities are introduced, the sintering degree is too high, the titanium substrate becomes compact, the pore diameter is small, the porosity is greatly reduced, and the application of the titanium alloy substrate as a gas diffusion layer is affected. Meanwhile, the addition of the metal oxide can raise the oxygen content in the system, so that the materials in the system are more easily oxidized. According to the invention, by using ammonium bicarbonate, sodium citrate and sodium stearate with the mass ratio of 1:0.3-0.5:0.1-0.3 as pore-forming agents in a matching manner, the oxidation of titanium alloy materials in a system is reduced, and the oxidation of titanium alloy is avoided to a certain extent because components such as sodium citrate have a certain reducibility, oxidizing components in the system are consumed.
The invention also provides a preparation method of the porous titanium alloy substrate, which comprises the following specific steps:
step S1: uniformly mixing titanium alloy powder, a pore-forming agent, metal oxide and metal fluoride in a mixer, and pressing into a blank by using a cold isostatic press;
step S2: placing the embryo in a vacuum or argon hot-pressing furnace, heating to 900-1300 ℃, preserving heat for 0.2-2h, and applying pressure of 0.5-1 ton; cutting the blank after cooling, polishing, pickling for 1-3h, washing with water to neutrality, and drying to obtain the final product.
In general, the smaller the particle size of the powder, the more contact interfaces between the powders, the faster the sintering speed, and the lower the sintering temperature, but at the same time, the denser. Therefore, the specific sintering grain size and the sintering temperature are matched, so that the high-efficiency sintering can be kept, and meanwhile, the certain porosity can be kept.
Preferably, the pressure of the cold isostatic press in step S1 is 80-120MPa. The titanium alloy powder is put into a grinding tool, and is pressed into a plate block by applying a certain pressure through a cold isostatic press. In the present invention, the shape of the pressed plate is not particularly limited, and a rectangular parallelepiped block is preferable. By means of specific pressing pressure, the titanium alloy powder is compactly accumulated, the contact area between particles is increased, sintering temperature can be reduced to a certain extent, and sintering efficiency is improved. However, if the pressing pressure is too high, the density of the titanium alloy powder is high, and the pore formation is affected.
The titanium alloy has very good heat conductivity, so the problem of uneven temperature is not easy to exist during sintering, but the side length of a blank body cannot be too large, otherwise, the sintering effect is affected. Preferably, the blank is a cuboid. More preferably, the cuboid has a width of 5-30cm, a length of 10-30cm, and a height of 10-30cm, and the length and the height are the same.
Preferably, the temperature rising rate in the step S2 is 8-10 ℃/min. The faster heating rate can avoid the overlength of heat preservation time and the rapid decomposition of pore-forming agent, which leads to the melting of pore diameter in the subsequent sintering process. But the rate of temperature rise cannot be too fast, otherwise too large an amount of gas may cause structural collapse.
Preferably, the acid solution used for the acid washing in step S2 is one of a hydrochloric acid solution, a sulfuric acid solution, and a nitric acid solution.
The acid solution used for pickling is not particularly limited in the invention, and can be selected by a person skilled in the art according to actual needs. Preferably, the acid solution is a hydrochloric acid solution of 0.1 to 0.5 mol/L.
Preferably, the cutting in step S2 is performed using a precision electric discharge machine. More preferably, the setting parameters of the precision electric discharge machine are: pulse width is 0.05 μs, pulse width is 0.3 μs, peak current is 2A.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses ammonium bicarbonate, sodium citrate and sodium stearate to prepare the pore agent, and has wide raw material sources and low cost; the prepared titanium alloy substrate has uniform pore distribution, and meanwhile, the formed pore diameter is mostly of a through hole structure, so that a transmission channel can be provided for gas, and the titanium alloy substrate has good air permeability.
(2) According to the invention, magnesium oxide and magnesium fluoride are added simultaneously, so that the sintering temperature can be effectively reduced, the production cost is reduced, and the prepared titanium alloy substrate has uniform pore diameter and higher porosity; and at the same time, maintains relatively excellent mechanical properties.
(3) According to the invention, the block-shaped titanium alloy substrate is cut into the thin sheet in a cutting mode, so that the surface is smooth and the flatness is high, and the problems of easiness in buckling deformation, easiness in cracking, poor flatness and the like in sintering after being pressed into the thin sheet in the prior art are solved. When used as a gas diffusion layer, the polymer film has good contact with proton films and the like, and avoids the problems of increasing contact resistance and the like.
(4) The titanium alloy powder used in the invention is coarse waste powder of the titanium alloy powder for 3D printing, thereby realizing effective utilization of titanium alloy resources and greatly saving cost; and raw materials such as titanium hydride powder and the like are avoided, so that the production is safer.
(5) After mixing and pressing the titanium alloy powder with a pore-forming agent, a metal oxide and a metal fluoride, the porous titanium alloy substrate is prepared by matching with a specific sintering process, has excellent acid and alkali resistance and corrosion resistance, excellent mechanical property and good conductivity, and simultaneously has rich and uniform pores. Particularly, when the porous material is used as a gas diffusion layer, excellent heat conduction and electric conductivity can be provided, and sufficient pores can also provide sufficient transmission channels for hydrogen, oxygen and the like while excellent mechanical properties are maintained. And the production cost is low, the preparation process is simple, and the quantitative production can be realized.
Drawings
FIG. 1 is an SEM image a of a porous titanium alloy substrate prepared according to example 1 of the present invention;
FIG. 2 is an SEM image b of a porous titanium alloy substrate according to example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments and the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
Example 1
The embodiment provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, which comprises the following raw materials in parts by weight: 93 parts of spherical titanium alloy powder, 6 parts of pore-forming agent, 2 parts of magnesium oxide and 1.5 parts of magnesium fluoride.
Wherein the spherical titanium alloy powder is TC4, purchased from Baozhen Chenyuan metal materials Co., ltd. The pore-forming agent is ammonium bicarbonate, sodium citrate and sodium stearate with the mass ratio of 1:0.4:0.2; mixing ammonium bicarbonate, sodium citrate and sodium stearate, and ball milling for 2 hours; ammonium bicarbonate, sodium citrate, and sodium stearate are purchased from national pharmaceutical group chemicals limited.
The average particle diameter of the magnesium oxide is 50nm, the purity is more than or equal to 99 percent, and the magnesium oxide is purchased from Xuan Chengjing Rui New Material Co., ltd; the particle size of magnesium fluoride is 200 mu m, the purity is more than or equal to 98 percent, and the magnesium fluoride is purchased from Shandong Hao chemical Co., ltd. Example 1 also provides a method for preparing a porous titanium alloy substrate based on spherical titanium alloy powder, comprising the following specific steps:
step S1: uniformly mixing titanium alloy powder, a pore-forming agent, metal oxide and metal fluoride in a mixer, and pressing into a cuboid blank by using a cold isostatic press (the pressure is 100 MPa), wherein the width of the cuboid is 15cm, and the length and the height are 20cm;
step S2: placing the embryo body in a vacuum hot-pressing furnace (the applied pressure in the hot-pressing furnace is 1 ton.), setting the heating rate to be 8 ℃/min, heating to 1100 ℃, and preserving heat for 1h; cooling to room temperature along with the furnace, cutting the plate into rectangular plates with the thickness of 2mm by using a precise electric spark cutting machine after cooling, polishing to more than 1000 meshes by using different sand paper, then using 0.3mol/L hydrochloric acid to carry out acid washing for 2 hours, washing to neutrality by water, and drying at 60 ℃ for 4 hours to obtain the product.
Wherein, the setting parameters of the precision electric spark cutting machine are as follows: pulse width is 0.05 μs, pulse width is 0.3 μs, peak current is 2A.
Example 2
The embodiment provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, which comprises the following raw materials in parts by weight: 96 parts of spherical titanium alloy powder, 8 parts of pore-forming agent, 3 parts of magnesium oxide and 2 parts of magnesium fluoride.
Wherein the spherical titanium alloy powder is TC4, purchased from Baozhen Chenyuan metal materials Co., ltd. The pore-forming agent is ammonium bicarbonate, sodium citrate and sodium stearate with the mass ratio of 1:0.4:0.2; mixing ammonium bicarbonate, sodium citrate and sodium stearate, and ball milling for 2 hours; ammonium bicarbonate, sodium citrate, and sodium stearate are purchased from national pharmaceutical group chemicals limited. The average particle diameter of the magnesium oxide is 50nm, the purity is more than or equal to 99 percent, and the magnesium oxide is purchased from Xuan Chengjing Rui New Material Co., ltd; the particle size of magnesium fluoride is 200 mu m, the purity is more than or equal to 98 percent, and the magnesium fluoride is purchased from Shandong Hao chemical Co., ltd.
The specific preparation method of example 2 is the same as that of example 1.
Example 3
The embodiment provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, which comprises the following raw materials in parts by weight: 90 parts of spherical titanium alloy powder, 3 parts of pore-forming agent, 1 part of magnesium oxide and 1 part of magnesium fluoride.
Wherein the spherical titanium alloy powder is TC4, purchased from Baozhen Chenyuan metal materials Co., ltd. The pore-forming agent is ammonium bicarbonate, sodium citrate and sodium stearate with the mass ratio of 1:0.4:0.2; mixing ammonium bicarbonate, sodium citrate and sodium stearate, and ball milling for 2 hours; ammonium bicarbonate, sodium citrate, and sodium stearate are purchased from national pharmaceutical group chemicals limited. The average particle diameter of the magnesium oxide is 50nm, the purity is more than or equal to 99 percent, and the magnesium oxide is purchased from Xuan Chengjing Rui New Material Co., ltd; the particle size of magnesium fluoride is 200 mu m, the purity is more than or equal to 98 percent, and the magnesium fluoride is purchased from Shandong Hao chemical Co., ltd.
The specific preparation method of example 3 is the same as that of example 1.
Example 4
The embodiment provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, and the specific implementation manner is the same as that of the embodiment 1, and the difference between the embodiment 1 and the embodiment 1 is that the pore-forming agent is ammonium bicarbonate, sodium citrate and sodium stearate with the mass ratio of 1:0.3:0.1.
Example 5
The specific implementation mode of the porous titanium alloy substrate prepared based on spherical titanium alloy powder is the same as that of the embodiment 1, and the difference between the specific implementation mode and the embodiment 1 is that the average grain diameter of magnesium oxide is 200nm, and the purity is more than or equal to 99%; the particle size of the magnesium fluoride is 400 meshes, and the purity is more than or equal to 98 percent.
Comparative example 1
The comparative example provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, and the specific embodiment is the same as example 1, and is different from example 1 in that the pore-forming agent is ammonium bicarbonate and sodium citrate in a mass ratio of 1:0.4.
Comparative example 2
This comparative example provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, and the specific embodiment is the same as example 1, and differs from example 1 in that the pore-forming agent is sodium citrate and sodium stearate in a mass ratio of 0.4:0.2.
Comparative example 3
The comparative example provides a porous titanium alloy substrate prepared based on spherical titanium alloy powder, and the specific embodiment is the same as example 1, and is different from example 1 in that the pore-forming agent is ammonium bicarbonate and sodium stearate in a mass ratio of 1:0.2.
Comparative example 4
This comparative example provides a porous titanium substrate prepared based on spherical titanium alloy powder, and the specific embodiment is the same as example 1, except that in the preparation process, the temperature rising rate in step S2 is 5 ℃/min.
Comparative example 5
This comparative example provides a porous titanium substrate prepared based on spherical titanium alloy powder, and the specific embodiment is different from example 1 in that the applied pressure in the autoclave is 3 tons.
Performance testing
1. Porosity test: the porosity is tested by adopting a relative density method, and the porosity calculation formula is as follows:
P＝1-m/Vρ s
wherein, P-porosity,%; m-mass of sample, g; v-volume of sample, cm 3 ；ρ s Density of sample matrix, g/cm 3 。
2. Average gas pore diameter: the test was performed according to the determination of the pore size of the bubble test, a permeable sintered metal material of GB/T5294-201X.
3. Compressive strength: the test is carried out according to the GB/T7314-2017 metal material room temperature compression test method.
4. Flatness: and testing by adopting a multifunctional profile measuring instrument.
5. Conductivity of: testing was performed using a four-probe tester.
6. Air permeability test: the material-air permeability measurements were performed according to GB/T31909 permeability sintering.
The above performance tests were conducted on examples 1 to 5 and comparative examples 1 to 5, and the test results are shown in Table 1 below.
TABLE 1
Fig. 1 and 2 are SEM images of a porous titanium substrate, and it can be seen from fig. 1 and 2 that the porous titanium alloy substrate prepared by the present invention has uniform pore diameter, abundant pores, and a large number of through-hole structures in the pores. As can be seen from the test data of table 1, when a sheet of 2mm is prepared, the porous titanium substrate still has high flatness, uniform pore size, high porosity, and excellent compressive strength, conductivity and other properties. Particularly when the porous material is used as a gas diffusion layer, the porous material can provide sufficient transmission channels for mediums such as hydrogen, oxygen and the like; the high flatness can be well contacted when the membrane electrode assembly is carried out, and the contact resistance is reduced; the sufficient compressive strength ensures that the support effect is stable enough. The porous titanium substrate prepared by the method has excellent comprehensive performance, low production cost and simple preparation process, and can realize quantitative production.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The porous titanium alloy substrate prepared based on the spherical titanium alloy powder is characterized in that the raw materials of the porous titanium alloy substrate comprise 90-96 parts by weight of the spherical titanium alloy powder, 3-8 parts by weight of a pore-forming agent, 1-3 parts by weight of a metal oxide and 1-2 parts by weight of a metal fluoride.
2. The porous titanium alloy substrate prepared based on spherical titanium alloy powder according to claim 1, wherein the spherical titanium alloy powder has an average particle size of 45-150um mesh and a purity of 99% or more.
3. The porous titanium alloy substrate prepared based on spherical titanium alloy powder according to claim 1, wherein the pore-forming agent is one or more of ammonium bicarbonate, ammonium carbonate, citric acid, sodium citrate, ammonium citrate, urea, sodium carbonate, magnesium carbonate, potassium carbonate, stearic acid, sodium stearate.
4. The porous titanium alloy substrate prepared based on spherical titanium alloy powder according to claim 3, wherein the pore-forming agent is ammonium bicarbonate, sodium citrate and sodium stearate, and the mass ratio of the ammonium bicarbonate, the sodium citrate and the sodium stearate is 1:0.3-0.5:0.1-0.3.
5. The porous titanium alloy substrate prepared based on spherical titanium alloy powder according to claim 1, wherein the metal oxide is one or a mixture of several of magnesium oxide, zinc oxide and yttrium oxide.
6. The porous titanium alloy substrate prepared based on spherical titanium alloy powder according to claim 1, wherein the metal fluoride is one or a mixture of several of magnesium fluoride, calcium fluoride and yttrium fluoride.
7. The method for producing a porous titanium alloy substrate based on spherical titanium alloy powder according to any one of claims 1 to 6, characterized in that the specific steps of the production method are as follows:
step S1: uniformly mixing titanium alloy powder, a pore-forming agent, metal oxide and metal fluoride in a mixer, and pressing into a blank by using a cold isostatic press;
step S2: placing the embryo in a vacuum or argon hot-pressing furnace, heating to 900-1300 ℃, preserving heat for 0.2-2h, and applying pressure of 0.5-1 ton; cutting the blank after cooling, polishing, pickling for 1-3h, washing with water to neutrality, and drying to obtain the final product.
8. The method for producing a porous titanium alloy substrate produced based on spherical titanium alloy powder according to claim 8, wherein the pressure of the cold isostatic press in step S1 is 80 to 120MPa.
9. The method for producing a porous titanium alloy substrate produced based on spherical titanium alloy powder according to claim 8, wherein the temperature rising rate in step S2 is 8 to 10 ℃/min.
10. The method for preparing a porous titanium alloy substrate based on spherical titanium alloy powder according to claim 8, wherein the acid solution used for pickling in step S2 is one of hydrochloric acid solution, sulfuric acid solution, and nitric acid solution.
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