CN115537632B - Titanium-nickel-iron-based alloy material and preparation method thereof - Google Patents

Titanium-nickel-iron-based alloy material and preparation method thereof Download PDF

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CN115537632B
CN115537632B CN202211181837.1A CN202211181837A CN115537632B CN 115537632 B CN115537632 B CN 115537632B CN 202211181837 A CN202211181837 A CN 202211181837A CN 115537632 B CN115537632 B CN 115537632B
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凌雨湘
何政浩
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Heyuan Yueao Cemented Carbide Co ltd
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Abstract

The invention provides a titanium-nickel-iron-based alloy material and a preparation method thereof, which belong to the technical field of hard alloy and comprise the following steps: s1, preparing porous hollow ferric oxide/nickel oxide microspheres; s2, preparing Fe-Ni-Al-Ti composite oxide; s3, reducing by hydrogen; s4, preparing a modified composite active additive; s5, molding and sintering. The titanium-nickel-iron alloy material prepared by the invention has the advantages of better oxidation resistance, high temperature resistance, corrosion resistance, good processing performance, less TCP phase formation, higher strength, better plasticity and toughness, long alloy lasting life, good ageing resistance and wide application prospect.

Description

Titanium-nickel-iron-based alloy material and preparation method thereof
Technical Field
The invention relates to the technical field of hard alloy, in particular to a titanium-nickel-iron-based alloy material and a preparation method thereof.
Background
The NS1402 alloy is a Ti-stabilized Ni-Fe-Cr-Mo-Cu corrosion resistant alloy, and the chemical composition and the weight percentage thereof are mainly C0.05%, si 0.5%, cr19.5-23.5%, ni38.0-46.0%, mo2.5-3.5%, mn 1.0%, cu1.5-3.0%, ti0.6-1.2%, S0.015%, P0.03%, al 0.2% and the balance Fe; the NS1402 alloy was developed by Inconel corporation in 1952 for the earliest times. The addition of the stabilizing element titanium in the NS1402 alloy can not only improve the stress corrosion resistance and fracture performance of the steel, but also greatly improve the corrosion resistance and the machinability of the steel in reducing acid, and the solid solution heat treatment state structure has good plasticity, strong toughness and easy cold working and forming, but has lower strength and hardness, and only improves the strength and the hardness through cold working deformation. The alloy has good corrosion resistance and is widely applied to industries such as chemical processing and the like.
Because the NS1402 alloy metal iron-nickel base high alloy material has poor hot working performance, high equipment requirements, in particular to the extrusion process or the inclined rolling perforation process in the pipe manufacturing process, the grasping degree of the hot working performance is dependent.
Because the NS1402 alloy is added with a large amount of refractory elements (including Mo, cr and the like) for solid solution strengthening, the high alloying can promote the precipitation of brittle harmful phases such as topological dense phase (TCO phase) and the like while improving the strength of the alloy, and the comprehensive performance of the alloy is reduced. In addition, segregation of refractory elements tends to occur during long-term heat exposure, also increasing the propensity of the TCP phase to precipitate. Common TCP phases are σ, laves and η equal. Mo is an element that strongly promotes the formation of sigma phase; cr also has the ability to promote the formation of sigma phase. On one hand, the existence of the TCP phase consumes a large amount of solid solution strengthening elements, so that the solid solution strengthening effect of the matrix is weakened; on the other hand, the needle-like or lamellar TCP phase is a channel where cracks originate and where cracks rapidly propagate. In the long-term use process of the high-temperature alloy, the precipitation of the TCP phase can reduce the plasticity and toughness of the alloy, and the aging of the long-term service life of the alloy is aggravated.
In conclusion, the novel titanium-nickel-iron-based alloy material which is easy to oxidize, high-temperature-resistant, corrosion-resistant, good in processing performance, capable of reducing TCP phase formation, improving alloy plasticity and toughness, prolonging alloy durability and aging-resistant needs to be developed and applied.
Disclosure of Invention
The invention aims to provide a titanium-nickel-iron-based alloy material and a preparation method thereof, which have the advantages of better oxidation resistance, high temperature resistance, corrosion resistance, good processing performance, less TCP phase formation, higher strength, better plasticity and toughness, long alloy lasting life, good ageing resistance and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a titanium-nickel-iron-based alloy material, which comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: dissolving nickel citrate, ferric citrate, a pore-forming agent and an emulsifying agent in water to obtain a water phase; adding the water phase into an organic solvent, emulsifying, heating and evaporating the solvent under the condition of continuously stirring, filtering, centrifuging, drying and calcining to obtain porous hollow ferric oxide/nickel oxide microspheres;
preferably, the organic solvent is at least one selected from dichloromethane, chloroform, ethyl acetate, methyl formate, and petroleum ether.
S2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving aluminum salt and titanium salt in water, adding the porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1 for uniform dispersion, then adding citric acid, heating and evaporating a solvent to form sol, continuously increasing the temperature, reducing the system pressure to form xerogel, igniting the xerogel, collecting combustion products, and ball-milling to obtain the Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, gradually heating, reducing and roasting a sample, and ball-milling to obtain a reduction product;
s4, preparing a modified composite active additive: mixing titanium boride, titanium phosphide and titanium carbide with 92# gasoline medium, and ball milling to obtain a modified composite active additive;
s5, molding and sintering: and (3) mixing the reduction product obtained in the step (S3) and the modified composite active additive obtained in the step (S4), performing ball milling, cold pressing, vacuum pressurizing and sintering, and performing two-stage heat treatment molding to obtain the titanium-nickel-iron-based alloy material.
As a further improvement of the invention, the mass ratio of the nickel citrate, the ferric citrate, the pore-forming agent and the emulsifying agent in the step S1 is 20-40:50-70:2-4:1-3; the mass ratio of the water phase to the organic solvent is 3-5:10; the emulsification condition is 10000-12000r/min for 5-10min; the temperature of the heated and evaporated solvent is 90-100 ℃ and the time is 0.5-1h; the stirring rotating speed is 1200-1500r/min; the calcination temperature is 500-700 ℃ and the time is 2-4h.
As a further improvement of the present invention, the porogen in step S1 includes a macroporous porogen, a mesoporous porogen, and a microporous porogen, the macroporous porogen being selected from at least one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether; the mesoporous pore-foaming agent is at least one selected from cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and ethylene oxide-propylene oxide triblock copolymer PEO106-PPO70-PEO 106; the micropore pore-forming agent is at least one selected from ammonium bicarbonate, isopropanol, silicone oil, lithium bromide and ammonium chloride; the emulsifier is at least one selected from Tween-20, tween-40, tween-60, tween-80, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate, sodium octadecyl sulfonate, and sodium octadecyl sulfate.
As a further improvement of the invention, the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio is 3-5:2-4:0.5-1.
As a further improvement of the present invention, the aluminum salt in step S2 is at least one selected from aluminum chloride, aluminum nitrate, aluminum sulfate; the titanium salt is at least one of titanium chloride, titanium nitrate and titanium sulfate; the mass ratio of the aluminum salt to the titanium salt to the citric acid to the porous hollow ferric oxide/nickel oxide microspheres is 0.7-1.2:0.5-1.5:3-5:90-100; the temperature of the heated and evaporated solvent is 80-90 ℃, the temperature is continuously increased to 160-180 ℃ in the heater, and the pressure of the system is reduced to 0.01-0.1MPa; the ball milling time is 1-2h.
As a further improvement of the invention, the purity of the hydrogen atmosphere in the step S3 is more than 99.5wt%, the flow is 100-120mL/min, the temperature is gradually raised to 1000-1200 ℃, the temperature raising rate is 10-15 ℃/min, the reduction roasting time is 2-4h, and the ball milling time is 0.5-1h.
As a further improvement of the invention, the mass ratio of the titanium boride, the titanium phosphide, the titanium carbide and the 92# gasoline medium in the step S4 is 0.2-0.5:1-3;3-5:5-10; the ball milling time is 1-2h.
As a further improvement of the invention, the mass ratio of the reduction product to the modified composite active additive in the step S5 is 100:1-3; the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650deg.C, sintering for 30-50min under 25-32MPa, heating from 650deg.C to 800deg.C, and sintering for 30-40min under 22-27MPa; the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1000-1050 ℃/20-30min, 1050-1100 ℃ 20-30min, 1100-1150 ℃/25-30h, air cooling to 720 ℃, and performing second-stage heat treatment: 720-770 ℃/1-2h and 780-800 ℃/22-24h, and air cooling to room temperature.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: dissolving 20-40 parts by weight of nickel citrate, 50-70 parts by weight of ferric citrate, 2-4 parts by weight of pore-forming agent and 1-3 parts by weight of emulsifier in 100 parts by weight of water to obtain a water phase; adding 3-5 parts by weight of water phase into 10 parts by weight of organic solvent, emulsifying for 5-10min at 10000-12000r/min, heating to 90-100 ℃ under stirring for evaporating the solvent for 0.5-1h at 1200-1500r/min, filtering, centrifuging, drying, calcining for 2-4h at 500-700 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio is 3-5:2-4:0.5-1;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 0.7-1.2 parts by weight of aluminum salt and 0.5-1.5 parts by weight of titanium salt in 200 parts by weight of water, adding 90-100 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 3-5 parts by weight of citric acid, heating to 80-90 ℃ to evaporate the solvent to form sol, continuously raising the temperature to 160-180 ℃ in a heater, reducing the system pressure to 0.01-0.1MPa to form xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1-2 hours to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 100-120mL/min, the temperature is gradually increased to 1000-1200 ℃, the temperature increasing rate is 10-15 ℃/min, the sample is subjected to reduction roasting for 2-4h, and the ball milling is carried out for 0.5-1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.2-0.5 weight part of titanium boride, 1-3 weight parts of titanium phosphide, 3-5 weight parts of titanium carbide and 5-10 weight parts of 92# gasoline medium, and ball milling for 1-2 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 1-3 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling, cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650deg.C, sintering for 30-50min under 25-32MPa, heating from 650deg.C to 800deg.C, and sintering for 30-40min under 22-27MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1000-1050 ℃/20-30min, 1050-1100 ℃ 20-30min, 1100-1150 ℃/25-30h, air cooling to 720 ℃, and performing second-stage heat treatment: 720-770 ℃/1-2h and 780-800 ℃/22-24h, and air cooling to room temperature.
The invention further protects the titanium-nickel-iron-based alloy material prepared by the preparation method.
The invention has the following beneficial effects:
the invention prepares a porous hollow ferric oxide/nickel oxide microsphere through a sol-gel method, firstly, nickel citrate, ferric citrate, a pore-forming agent and an emulsifying agent are dissolved in water to obtain a water phase, the water phase is added into an organic solvent to be emulsified to obtain oil-in-water microsphere emulsion liquid drops, the solvent is heated and evaporated to enable the organic solvent to volatilize rapidly, thereby forming gel liquid drops, and the porous hollow ferric oxide/nickel oxide microsphere is obtained after filtration, drying and calcination;
The pore-forming agent comprises a macroporous pore-forming agent, a mesoporous pore-forming agent and a microporous pore-forming agent, and under the synergistic effect of the macroporous pore-forming agent, the mesoporous pore-forming agent and the microporous pore-forming agent, a large number of macropore (more than 50 nm) pore channels, mesoporous (2-50 nm) pore channels and microporous (less than 2 nm) pore channels are formed on the surface of the prepared porous hollow ferric oxide/nickel oxide microsphere, so that the subsequent dissolution of other metal and nonmetal elements is facilitated, the component elements can fully enter the porous hollow ferric oxide/nickel oxide microsphere to form an organism, and various elements can fully and organically fuse together in the subsequent hydrogenation reduction, so that the comprehensive performance of the titanium-nickel-iron alloy is improved.
Dissolving aluminum salt and titanium salt in water, adding porous hollow ferric oxide/nickel oxide microspheres, adding citric acid to form citric acid-aluminum and citric acid-titanium complex, entering the microspheres, evaporating solvent to form sol, further increasing the temperature to form xerogel, and carrying out oxidation reaction in the ignition process to obtain Fe-Ni-Al-Ti composite oxide;
the modified composite active additive comprises titanium boride, titanium phosphide and titanium carbide, and the active additive is directly added to be easy to agglomerate and not uniformly dispersed in the alloy material, and an organic film layer is formed on the surface through gasoline ball milling treatment, so that the agglomeration is avoided, the active additive can be well dispersed in the alloy material, some Ti, B, P, C elements are reasonably distributed in the alloy material, and the comprehensive performance of the alloy material is improved.
The invention takes iron as alloy matrix, can obviously reduce the cost of composite materials, and simultaneously adds a large amount of nickel into the alloy to enlarge the austenite range of the alloy, so as to form stable austenite alloy, and in addition, the nickel can form gamma' precipitation phase with Al, ti and other elements, thereby achieving the strengthening purpose of nickel-based superalloy. To a certain extent, the content of Fe element in the alloy is reduced, co element is used for replacing part of Fe element, gamma ' phase volume fraction in the alloy is reduced, gamma ' phase precipitation strengthening is adopted, failure risk caused by unstable transformation of gamma ' phase at the temperature of over 650 ℃ is reduced in the alloy, the use temperature of the alloy is greatly improved, and Co is added to cause larger lattice distortion with iron base, so that stress field is generated, and the strength of the alloy is improved.
The trace elements of the invention, including Ti, al, P, C, can purify grain boundary, improve strength and plasticity of the grain boundary, improve high-temperature durability of the alloy, and improve oxidation resistance and corrosion resistance of the alloy.
The invention can generate a layer of continuous compact aluminum oxide (Al) with good adhesiveness on the surface of alloy material by adding Al with proper proportion into the alloy 2 O 3 ) The film has the protection effect on the alloy and improves the anti-corrosion and anti-oxidation performance. By adding Al element, a high-temperature alloy gamma' phase is formed, and the alloy has a strengthening effect. Can also react with the element nickel with larger content to generate gamma' phase Ni 3 Al phase is separated out, and the existence of gamma' phase can prevent dislocation movement of alloy, so that the strength of alloy is obviously improved. Meanwhile, when the alloy is in a saline-alkali environment, na 2 SO 4 Molten salt is condensed in Al 2 O 3 Al on oxide film 2 O 3 The molten salt and the oxide film coexist to improve the heat resistance and corrosion resistance of the alloy.
The alloy of the invention is additionally added with a proper amount of Ti element, and Ti is also one of main elements forming gamma' phase, thereby achieving the purpose of solid solution strengthening. Meanwhile, when Ti and Al are simultaneously present in an alloy, ti also has a promoting effect on the precipitation of gamma' phase. Ti can also form a stable TiC phase, so that the strength of the alloy is improved.
The second phase in the superalloy may retard dislocation movement of the alloy, effecting alloy strengthening. The addition of Al, ti and other elements forms a certain amount of gamma' phase, which plays a good role in strengthening the high-temperature alloy.
The C element can form carbide in the alloy, the carbide is precipitated in a crystal boundary to prevent migration of the crystal boundary, the grain size can be controlled, crack propagation is prevented, and the performance of the alloy is improved, but the carbide also becomes a stress concentration area and a crack source.
M 23 C 6 The temperatures present in the superalloy range from 650 ℃ to 1100 ℃, usually starting to precipitate at 650 ℃, reaching 800 ℃ to 900 ℃ as a precipitation peak, and when starting to dissolve above 900 ℃, essentially already melt into the substrate at 1050 ℃. In the preparation process of the alloy, a two-stage heat treatment process is adopted, wherein the second-stage heat treatment is 720 ℃/1h,780 ℃/24h and then air cooling is carried out, and the purpose is to precipitate a large amount of chain M 23 C 6 To strengthen the alloy. The carbide forms discontinuous granular carbide at the grain boundary to prevent the sliding and crack growth of the grain boundary, and the durability and the plasticity and toughness of the alloy are improved.
Deformation under the action of the lasting stress is mainly concentrated in the crystal grains, the crystal grains are elongated, and meanwhile, the stress at the crystal boundary is relaxed, so that the formation of crystal boundary cracks is slowed down, the fracture form of the alloy is changed from a crystal form to a mixed crystal form, the influence of B on the properties of the high-temperature alloy such as stretching, lasting and creep is obvious, boride particles precipitated at the crystal boundary can effectively prevent the crystal boundary from sliding and inhibit the connection and the expansion among crystal boundary cavities; at the same time, boron also eliminates the deleterious phases at the grain boundaries and reduces the levels of deleterious elements.
P is a surface active element, is insoluble in matrix gamma phase and gamma' strengthening phase, and can only be partially polymerized at defects such as grain boundary or dislocation. The P which is partially gathered at the dislocation position can form air clusters to play a role in preventing dislocation movement, so that the P can be partially gathered at the dislocation and the grain boundary to influence the intra-crystal and grain boundary strength of the alloy, thereby improving the precipitation of the grain boundary, preventing oxygen in the environment from invading along the grain boundary to cause cracking, and improving the diffusion activation energy of the grain boundary.
The titanium-nickel-iron alloy material prepared by the invention has the advantages of better oxidation resistance, high temperature resistance, corrosion resistance, good processing performance, less TCP phase formation, higher strength, better plasticity and toughness, long alloy lasting life, good ageing resistance and wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is an SEM image of the Fe-Ni-Al-Ti composite oxide according to step S2 of example 1 of the present invention;
FIG. 2 is a diagram showing a metallographic structure of the first heat treatment in step S5 of example 1 of the present invention;
FIG. 3 is a diagram showing a metallographic structure of the second heat treatment in step S5 of example 1 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only 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.
Example 1
The embodiment provides a preparation method of a titanium-nickel-iron-based alloy material, which specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: dissolving 20 parts by weight of nickel citrate, 50 parts by weight of ferric citrate, 2 parts by weight of a pore-forming agent and 1 part by weight of sodium dodecyl sulfate in 100 parts by weight of water to obtain a water phase; adding 3 parts by weight of water phase into 10 parts by weight of petroleum ether, emulsifying for 5min at 10000r/min, heating to 90 ℃ under stirring for 0.5h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 2h at 500 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 3:2:0.5;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 0.7 weight part of aluminum sulfate and 0.5 weight part of titanium sulfate in 200 weight parts of water, adding 90 weight parts of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 3 weight parts of citric acid, heating to 80 ℃ to evaporate solvent to form sol, continuously increasing the temperature to 160 ℃ in a heater, reducing the system pressure to 0.01MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball milling for 1h to obtain Fe-Ni-Al-Ti composite oxide; FIG. 1 is an SEM image of the Fe-Ni-Al-Ti composite oxide thus obtained.
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 100mL/min, the temperature is gradually increased to 1000 ℃, the temperature increasing rate is 10 ℃/min, the sample is subjected to reduction roasting for 2 hours, and the ball milling is carried out for 0.5 hour, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.2 part by weight of titanium boride, 1 part by weight of titanium phosphide, 3 parts by weight of titanium carbide and 5 parts by weight of 92# gasoline medium, and ball milling for 1h to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 1 part by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 30min, wherein the pressure is 25MPa, heating from 650 ℃ to 800 ℃, and sintering for 30min, wherein the pressure is 22MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1000 ℃/20min, 1050 ℃ 20min, 1100 ℃/25h, air cooling to 720 ℃, and performing second-stage heat treatment: 720 ℃/1h and 780 ℃/22h, and air cooling to room temperature. FIG. 2 is a diagram of a metallographic structure after a first heat treatment, wherein small grains are gathered and distributed around large grains, and the area ratio of the small grains is larger than that of the large grains; FIG. 3 is a diagram of a metallographic structure after a second heat treatment, wherein the uniformity of grain growth is improved, the area ratio of small-size grains is greatly reduced by increasing the heat treatment temperature and prolonging the heat preservation time, and the grown grains are mainly equiaxed grains.
Example 2
The embodiment provides a preparation method of a titanium-nickel-iron-based alloy material, which specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 40 parts by weight of nickel citrate, 70 parts by weight of ferric citrate, 4 parts by weight of pore-forming agent and 3 parts by weight of sodium stearyl benzene sulfonate are dissolved in 100 parts by weight of water to obtain a water phase; adding 5 parts by weight of water phase into 10 parts by weight of ethyl acetate, emulsifying for 10min at 12000r/min, heating to 100 ℃ under stirring at 1500r/min to evaporate the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 4h at 700 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio is 5:4:1;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1.2 parts by weight of aluminum chloride and 1.5 parts by weight of titanium chloride in 200 parts by weight of water, adding 100 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 5 parts by weight of citric acid, heating to 90 ℃ to evaporate the solvent to form sol, continuously increasing the temperature to 180 ℃ in a heater, reducing the system pressure to 0.1MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball milling for 2 hours to obtain Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 120mL/min, the temperature is gradually increased to 1200 ℃, the temperature increasing rate is 15 ℃/min, and the sample is subjected to reduction roasting for 4 hours and ball milling for 1 hour to obtain a reduction product;
s4, preparing a modified composite active additive: mixing 0.5 weight part of titanium boride, 3 weight parts of titanium phosphide and 5 weight parts of titanium carbide with 10 weight parts of 92# gasoline medium, and ball milling for 2 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 3 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 50min, wherein the pressure is 32MPa, heating from 650 ℃ to 800 ℃, and sintering for 40min, wherein the pressure is 27MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1050 ℃/30min, 1100 ℃ 30min, 1150 ℃/30h, air-cooling to 720 ℃, and performing second-stage heat treatment: 770 ℃/2h and 800 ℃/24h, and air cooling to room temperature.
Example 3
The embodiment provides a preparation method of a titanium-nickel-iron-based alloy material, which specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Example 4
In comparison with example 3, the porogen was only a single polyoxyethylene sorbitan fatty acid ester, and the other conditions were not changed.
Example 5
In contrast to example 3, the porogen was only a single cetyltrimethylammonium bromide, with no change in other conditions.
Example 6
In contrast to example 3, the porogen was only a single lithium bromide, with no change in other conditions.
Comparative example 1
In contrast to example 3, no porogen was added in step S1 and the other conditions were unchanged.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 2
In contrast to example 3, no aluminum nitrate was added in step S2, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Ti composite oxide: dissolving 2 parts by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate the solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the system pressure to 0.05MPa to form xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the heating rate is 12 ℃/min, the sample is subjected to reduction roasting for 3h, and the ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 3
In contrast to example 3, no titanium nitrate was added in step S2, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al composite oxide: dissolving 2 parts by weight of aluminum nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate the solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the system pressure to 0.05MPa to form xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the heating rate is 12 ℃/min, the sample is subjected to reduction roasting for 3h, and the ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 4
In comparison with example 3, step S2 was not included, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s3, hydrogen reduction: placing the porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the heating rate is 12 ℃/min, the sample is subjected to reduction roasting for 3h, and the ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 5
In contrast to example 3, no titanium boride was added in step S4, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 2 parts by weight of titanium phosphide, 4 parts by weight of titanium carbide and 7 parts by weight of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 6
In contrast to example 3, no titanium phosphide was added in step S4, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 7
In contrast to example 3, no titanium carbide was added in step S4, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 8
In comparison with example 3, no 92# gasoline modification was added in step S4, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide and 4 weight parts of titanium carbide, and ball milling for 1.5 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 9
In comparison with example 3, step S4 was not included, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, molding and sintering: ball milling the reduction product obtained in the step S3 for 2 hours, cold pressing at 25MPa, vacuum pressurizing and sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
The conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, air cooling to 720 ℃, and performing second-stage heat treatment: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 10
In contrast to example 3, the first stage heat treatment was not included in step S5, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
S2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing heat treatment forming to obtain a titanium-nickel-iron-based alloy material;
The conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the conditions for the heat treatment molding are as follows: 750 ℃/1.5h and 790 ℃/23h, and air cooling to room temperature.
Comparative example 11
In contrast to example 3, the second stage heat treatment was not included in step S5, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 2 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, performing vacuum pressure sintering, and performing heat treatment forming to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650 ℃, sintering for 40min, wherein the pressure is 27MPa, heating from 650 ℃ to 800 ℃, and sintering for 35min, wherein the pressure is 25MPa;
the conditions for the heat treatment molding are as follows: 1025 ℃/25min, 1075 ℃ 25min, 1125 ℃/27h, and air cooling to room temperature.
Comparative example 12
In contrast to example 3, the two-stage heat treatment molding was not included in step S5, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: 30 parts by weight of nickel citrate, 60 parts by weight of ferric citrate, 3 parts by weight of pore-forming agent and 2 parts by weight of tween-80 are dissolved in 100 parts by weight of water to obtain a water phase; adding 4 parts by weight of water phase into 10 parts by weight of dichloromethane, emulsifying for 7min at 11000r/min, heating to 95 ℃ under stirring for evaporating the solvent for 1h, filtering, centrifuging for 15min at 5000r/min, drying for 2h at 70, and calcining for 3h at 600 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the cetyl trimethyl ammonium bromide to the lithium bromide is 4:3:0.7;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 1 part by weight of aluminum nitrate and 1 part by weight of titanium nitrate in 200 parts by weight of water, adding 95 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 4 parts by weight of citric acid, heating to 85 ℃ to evaporate a solvent to form sol, continuously increasing the temperature to 170 ℃ in a heater, reducing the pressure of the system to 0.05MPa, forming xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1.5h to obtain Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 110mL/min, the temperature is gradually increased to 1100 ℃, the temperature increasing rate is 12 ℃/min, reducing roasting is carried out on a sample for 3h, and ball milling is carried out for 1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.35 weight part of titanium boride, 2 weight parts of titanium phosphide, 4 weight parts of titanium carbide and 7 weight parts of 92# gasoline medium, and ball milling for 1.5 hours to obtain a modified composite active additive;
s5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 3 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling for 2 hours, performing 25MPa cold pressing, and performing vacuum pressure sintering to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: after the temperature is raised to 650 ℃ from room temperature, sintering is carried out for 50min, the pressure is 32MPa, and after the temperature is raised to 800 ℃ from 650 ℃, sintering is carried out for 40min, and the pressure is 27MPa.
Test example 1
The titanium-nickel-iron-based alloy materials prepared in examples 1 to 6 and comparative examples 1 to 12 were processed into test pieces having a length X width X height of 70mm X50 mm X15 mm, respectively, and were subjected to an instantaneous tensile test and a long-term permanent tensile test, wherein the tensile tester used for the instantaneous tensile test was DSC-25J in type, and subjected to a room temperature tensile test, and SHIMADZU AG-250KNE in type, and subjected to a high temperature tensile test. The model of the electronic creep endurance tester adopted in the long-time endurance tensile test is CSS-3905.
The test conditions for the instantaneous stretching were stretching at five temperatures of room temperature, 450 ℃, 650 ℃, 850 ℃ and 950 ℃ respectively, with the stretching loading rate unchanged. Long-term permanent tensile tests were carried out at 750 ℃ under 6 different stresses, respectively: 550MPa, 500MPa, 450MPa, 400MPa, 350MPa and 300MPa.
The results are shown in tables 1 and 2.
TABLE 1
Figure BDA0003867107330000291
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Figure BDA0003867107330000301
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Figure BDA0003867107330000311
TABLE 2
Figure BDA0003867107330000312
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Figure BDA0003867107330000321
As can be seen from the table, the titanium-nickel-iron-based alloy materials prepared in the embodiments 1-3 have the mechanical properties of room temperature and high temperature, and have long lasting fracture time at high temperature and good durability in use.
In examples 4, 5 and 6, the pore-forming agent was only a single polyoxyethylene sorbitan fatty acid ester, cetyltrimethylammonium bromide and lithium bromide, and the mechanical properties thereof were reduced and the duration of fracture was shortened, as compared with example 3. Compared with the embodiment 3, the comparative example 1 has obviously reduced mechanical properties and obviously shortened lasting fracture time without adding pore-forming agent in the step S1. The pore-forming agent comprises a macroporous pore-forming agent, a mesoporous pore-forming agent and a microporous pore-forming agent, and under the synergistic effect of the macroporous pore-forming agent, the mesoporous pore-forming agent and the microporous pore-forming agent, a large number of macropore (more than 50 nm) pore channels, mesoporous (2-50 nm) pore channels and microporous (less than 2 nm) pore channels are formed on the surface of the prepared porous hollow ferric oxide/nickel oxide microsphere, so that the subsequent dissolution of other metal and nonmetal elements is facilitated, the component elements can fully enter the porous hollow ferric oxide/nickel oxide microsphere to form an organism, and various elements can fully and organically fuse together in the subsequent hydrogenation reduction, so that the comprehensive performance of the titanium-nickel-iron alloy is improved.
In comparative examples 2 and 3, in comparison with example 3, aluminum nitrate or titanium nitrate was not added in step S2. Compared with the example 3, the comparative example 4 does not comprise the step S2, the high-temperature mechanical property is obviously reduced, and the lasting fracture time is shortened. By adding Al element, a high-temperature alloy gamma' phase is formed, and the alloy has a strengthening effect. Can also react with the element nickel with larger content to generate gamma' phase Ni 3 Al phase is separated out, and the existence of gamma' phase can prevent dislocation movement of alloy, so that the strength of alloy is obviously improved. The alloy of the invention is additionally added with a proper amount of Ti element, and Ti is also one of main elements forming gamma' phase, thereby achieving the purpose of solid solution strengthening. Meanwhile, when Ti and Al are simultaneously present in an alloy, ti also has a promoting effect on the precipitation of gamma' phase. Ti can also form a stable TiC phase, so that the strength of the alloy is improved. The second phase in the superalloy may retard dislocation movement of the alloy, effecting alloy strengthening. The addition of Al, ti and other elements forms a certain amount of gamma' phase, which plays a good role in strengthening the high-temperature alloy.
Comparative examples 5, 6 and 7 were reduced in mechanical properties of comparative examples 6 and 7, and in high temperature mechanical properties of comparative example 5, and in the duration of fracture of 3 comparative examples, there was a different degree of reduction, as compared with example 3, in which no titanium boride, titanium phosphide or titanium carbide was added in step S4. Compared with example 3, the mechanical properties of comparative example 9 are obviously reduced and the duration of fracture is obviously shortened without step S4. The C element can form carbide in the alloy, the carbide is precipitated in a crystal boundary to prevent migration of the crystal boundary, the grain size can be controlled, crack propagation is prevented, and the performance of the alloy is improved, but the carbide also becomes a stress concentration area and a crack source. Deformation under the action of the lasting stress is mainly concentrated in the crystal grains, the crystal grains are elongated, and meanwhile, the stress at the crystal boundary is relaxed, so that the formation of crystal boundary cracks is slowed down, the fracture form of the alloy is changed from a crystal form to a mixed crystal form, the influence of B on the properties of the high-temperature alloy such as stretching, lasting and creep is obvious, boride particles precipitated at the crystal boundary can effectively prevent the crystal boundary from sliding and inhibit the connection and the expansion among crystal boundary cavities; at the same time, boron also eliminates the deleterious phases at the grain boundaries and reduces the levels of deleterious elements. P is a surface active element, is insoluble in matrix gamma phase and gamma' strengthening phase, and can only be partially polymerized at defects such as grain boundary or dislocation. The P which is partially gathered at the dislocation position can form air clusters to play a role in preventing dislocation movement, so that the P can be partially gathered at the dislocation and the grain boundary to influence the intra-crystal and grain boundary strength of the alloy, thereby improving the precipitation of the grain boundary, preventing oxygen in the environment from invading along the grain boundary to cause cracking, and improving the diffusion activation energy of the grain boundary.
Compared with the comparative example 3, the mechanical properties of the modified gasoline in the step S4 are reduced and the durable breaking time is shortened without adding the modified gasoline 92# in the step S4. The modified composite active additive comprises titanium boride, titanium phosphide and titanium carbide, wherein the titanium boride, titanium phosphide or titanium carbide is added into the material, the active additive is directly added to form agglomeration and cannot be uniformly dispersed in the alloy material, and an organic film layer is formed on the surface through ball milling treatment of gasoline, so that the agglomeration is avoided, the active additive can be well dispersed in the alloy material, some Ti, B, P, C elements are reasonably distributed in the alloy material, and the comprehensive performance of the alloy material is improved.
Comparative examples 10 and 11 did not include the first stage heat treatment or the second stage heat treatment in step S5, as compared with example 3. Compared with the embodiment 3, the comparative example 12 does not comprise two-stage heat treatment molding in the step S5, the mechanical property is slightly reduced, and the lasting fracture time is obviously shortened. M is M 23 C 6 The temperatures present in the superalloy range from 650 ℃ to 1100 ℃, usually starting to precipitate at 650 ℃, reaching 800 ℃ to 900 ℃ as a precipitation peak, and when starting to dissolve above 900 ℃, essentially already melt into the substrate at 1050 ℃. In the preparation process of the alloy, a two-stage heat treatment process is adopted, wherein the second-stage heat treatment is 720 ℃/1h,780 ℃/24h and then air cooling is carried out, and the purpose is to precipitate a large amount of chain M 23 C 6 To strengthen the alloy. The formation of discontinuous particulate carbides at the grain boundaries prevents the grain boundariesSliding and crack propagation, and the durability and the plasticity and toughness of the alloy are improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The preparation method of the titanium-nickel-iron-based alloy material is characterized by comprising the following steps of:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: dissolving nickel citrate, ferric citrate, a pore-forming agent and an emulsifying agent in water to obtain a water phase; adding the water phase into an organic solvent, emulsifying, heating and evaporating the solvent under the condition of continuously stirring, filtering, centrifuging, drying and calcining to obtain porous hollow ferric oxide/nickel oxide microspheres;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving aluminum salt and titanium salt in water, adding the porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1 for uniform dispersion, then adding citric acid, heating and evaporating a solvent to form sol, continuously increasing the temperature, reducing the system pressure to form xerogel, igniting the xerogel, collecting combustion products, and ball-milling to obtain the Fe-Ni-Al-Ti composite oxide;
S3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, gradually heating, reducing and roasting a sample, and ball-milling to obtain a reduction product;
s4, preparing a modified composite active additive: mixing titanium boride, titanium phosphide and titanium carbide with 92# gasoline medium, and ball milling to obtain a modified composite active additive;
s5, molding and sintering: and (3) mixing the reduction product obtained in the step (S3) and the modified composite active additive obtained in the step (S4), performing ball milling, cold pressing, vacuum pressurizing and sintering, and performing two-stage heat treatment molding to obtain the titanium-nickel-iron-based alloy material.
2. The preparation method according to claim 1, wherein the mass ratio of the nickel citrate, the ferric citrate, the pore-forming agent and the emulsifier in the step S1 is 20-40:50-70:2-4:1-3; the mass ratio of the water phase to the organic solvent is 3-5:10; the emulsification condition is 10000-12000r/min for 5-10min; the temperature of the heated and evaporated solvent is 90-100 ℃ and the time is 0.5-1h; the stirring rotating speed is 1200-1500r/min; the calcination temperature is 500-700 ℃ and the time is 2-4h.
3. The preparation method according to claim 1, wherein the porogen in step S1 comprises a macroporous porogen, a mesoporous porogen and a microporous porogen, and the macroporous porogen is at least one selected from polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether; the mesoporous pore-foaming agent is at least one selected from cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and ethylene oxide-propylene oxide triblock copolymer PEO106-PPO70-PEO 106; the micropore pore-forming agent is at least one selected from ammonium bicarbonate, isopropanol, silicone oil, lithium bromide and ammonium chloride; the emulsifier is at least one selected from Tween-20, tween-40, tween-60, tween-80, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate, sodium octadecyl sulfonate, and sodium octadecyl sulfate.
4. The preparation method according to claim 3, wherein the pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyltrimethylammonium bromide and lithium bromide in a mass ratio of 3-5:2-4:0.5-1.
5. The method according to claim 1, wherein the aluminum salt in step S2 is at least one selected from the group consisting of aluminum chloride, aluminum nitrate, and aluminum sulfate; the titanium salt is at least one of titanium chloride, titanium nitrate and titanium sulfate; the mass ratio of the aluminum salt to the titanium salt to the citric acid to the porous hollow ferric oxide/nickel oxide microspheres is 0.7-1.2:0.5-1.5:3-5:90-100; the temperature of the heated and evaporated solvent is 80-90 ℃, the temperature is continuously increased to 160-180 ℃ in the heater, and the pressure of the system is reduced to 0.01-0.1MPa; the ball milling time is 1-2h.
6. The preparation method according to claim 1, wherein the purity of the hydrogen atmosphere in the step S3 is greater than 99.5wt%, the flow is 100-120mL/min, the gradual temperature rise is 1000-1200 ℃, the temperature rise rate is 10-15 ℃/min, the reduction roasting time is 2-4h, and the ball milling time is 0.5-1h.
7. The method according to claim 1, wherein the mass ratio of titanium boride, titanium phosphide, titanium carbide and 92# gasoline medium in step S4 is 0.2-0.5:1-3;3-5:5-10; the ball milling time is 1-2h.
8. The preparation method according to claim 1, wherein the mass ratio of the reduction product and the modified composite active additive in the step S5 is 100:1-3; the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650deg.C, sintering for 30-50min under 25-32MPa, heating from 650deg.C to 800deg.C, and sintering for 30-40min under 22-27MPa; the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1000-1050 ℃/20-30min, 1050-1100 ℃ 20-30min, 1100-1150 ℃/25-30h, air cooling to 720 ℃, and performing second-stage heat treatment: 720-770 ℃/1-2h and 780-800 ℃/22-24h, and air cooling to room temperature.
9. The preparation method according to claim 1, characterized by comprising the following steps:
s1, preparing porous hollow ferric oxide/nickel oxide microspheres: dissolving 20-40 parts by weight of nickel citrate, 50-70 parts by weight of ferric citrate, 2-4 parts by weight of pore-forming agent and 1-3 parts by weight of emulsifier in 100 parts by weight of water to obtain a water phase; adding 3-5 parts by weight of water phase into 10 parts by weight of organic solvent, emulsifying for 5-10min at 10000-12000r/min, heating to 90-100 ℃ to evaporate the solvent for 0.5-1h under the stirring condition of 1200-1500r/min, filtering, centrifuging, drying, calcining for 2-4h at 500-700 ℃ to obtain porous hollow ferric oxide/nickel oxide microspheres;
The pore-forming agent comprises polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide and lithium bromide, wherein the mass ratio is 3-5:2-4:0.5-1;
s2, preparation of Fe-Ni-Al-Ti composite oxide: dissolving 0.7-1.2 parts by weight of aluminum salt and 0.5-1.5 parts by weight of titanium salt in 200 parts by weight of water, adding 90-100 parts by weight of porous hollow ferric oxide/nickel oxide microspheres prepared in the step S1, uniformly dispersing, then adding 3-5 parts by weight of citric acid, heating to 80-90 ℃ to evaporate the solvent to form sol, continuously raising the temperature to 160-180 ℃ in a heater, reducing the system pressure to 0.01-0.1MPa to form xerogel, igniting the xerogel, collecting combustion products, and ball-milling for 1-2 hours to obtain Fe-Ni-Al-Ti composite oxide;
s3, hydrogen reduction: placing the Fe-Ni-Al-Ti composite oxide prepared in the step S3 in a hydrogen atmosphere, wherein the purity of the hydrogen atmosphere is more than 99.5wt%, the flow is 100-120mL/min, the temperature is gradually increased to 1000-1200 ℃, the temperature increasing rate is 10-15 ℃/min, the sample is subjected to reduction roasting for 2-4h, and the ball milling is carried out for 0.5-1h, so that a reduction product is obtained;
s4, preparing a modified composite active additive: mixing 0.2-0.5 weight part of titanium boride, 1-3 weight parts of titanium phosphide, 3-5 weight parts of titanium carbide and 5-10 weight parts of 92# gasoline medium, and ball milling for 1-2 hours to obtain a modified composite active additive;
S5, molding and sintering: mixing 100 parts by weight of the reduction product prepared in the step S3 and 1-3 parts by weight of the modified composite active additive prepared in the step S4, performing ball milling, cold pressing, performing vacuum pressure sintering, and performing two-stage heat treatment molding to obtain a titanium-nickel-iron-based alloy material;
the conditions of the vacuum pressure sintering are as follows: heating from room temperature to 650deg.C, sintering for 30-50min under 25-32MPa, heating from 650deg.C to 800deg.C, and sintering for 30-40min under 22-27MPa;
the two-stage heat treatment molding conditions are as follows: first stage heat treatment: 1000-1050 ℃/20-30min, 1050-1100 ℃ 20-30min, 1100-1150 ℃/25-30h, air cooling to 720 ℃, and performing second-stage heat treatment: 720-770 ℃/1-2h and 780-800 ℃/22-24h, and air cooling to room temperature.
10. A titanium-nickel-iron-based alloy material produced by the production method according to any one of claims 1 to 9.
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