CN106244889B - A kind of TiCuAlCrMoNi high-entropy alloys and preparation method thereof - Google Patents
A kind of TiCuAlCrMoNi high-entropy alloys and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 139
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 205
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims description 82
- 239000010949 copper Substances 0.000 claims description 68
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 46
- 239000010936 titanium Substances 0.000 claims description 38
- 229910011214 Ti—Mo Inorganic materials 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 230000005672 electromagnetic field Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 25
- 238000005260 corrosion Methods 0.000 abstract description 25
- 239000013535 sea water Substances 0.000 abstract description 18
- 230000007812 deficiency Effects 0.000 abstract 1
- 230000003373 anti-fouling effect Effects 0.000 description 17
- 229910052804 chromium Inorganic materials 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 238000010828 elution Methods 0.000 description 6
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
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- 241001062472 Stokellia anisodon Species 0.000 description 1
- 229910010165 TiCu Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- -1 and meanwhile Substances 0.000 description 1
- 238000010314 arc-melting process Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
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- C22C1/03—Making non-ferrous alloys by melting using master alloys
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Abstract
A kind of TiCuAlCrMoNi high-entropy alloys and preparation method thereof, the component of the high-entropy alloy is TiaCubAlcCrdMoeNif, wherein, a, b, c, d, e and f represent the mol ratio of corresponding each element, 0.3≤a≤1.5,0.2≤b≤1.2,0.2≤c≤1.5,0.05≤d≤1.2,0≤e≤1.2,0.05≤f≤1.2 respectively.The present invention prepares microhardness not less than 550HV, seawater corrosion resistance, the high entropy alloy material for possessing certain anti-pollution function by non-consumable vacuum arc melting technique or electromagnetic levitation-melt technique, the deficiency of traditional high-entropy alloy is made up, meets following Marine Materials application demand.
Description
Technical Field
The invention relates to the technical field of high-entropy alloys, in particular to a TiCuAlCrMoNi high-entropy alloy and a preparation method thereof.
Background
The seawater pipeline system is distributed at each part of the ship, mainly provides cooling seawater and fire water for the whole ship, provides ballast water required by a ship ballast water system, ensures the normal operation of key equipment of the ship, has large quantity, small intervals and complex maintenance, is mostly in the severe environment with humidity, high temperature and high salinity, and has severe service working condition. The titanium alloy has the advantages of small density, high specific strength, no magnetism, seawater corrosion resistance and the like, and has wide application prospect in the field of ships. The yield strength of the existing titanium and titanium alloy for ships is generally below 1150MPa, and the application requirement of deep sea equipment on high-strength titanium alloy cannot be met; titanium has good biocompatibility and is easy to cause marine organism pollution damage, and when marine organisms are accumulated on the inner wall of the seawater pipeline, parts such as the pipeline, a pump, a valve, a heat exchanger and the like are blocked, so that the flow rate and the heat exchange efficiency of seawater are influenced.
High Entropy alloy (High Entropy alloy) is a new alloy design concept proposed in the 90 s of the 20 th century, also called High chaos alloy, which is an alloy characterized in that various metal elements all occupy High atomic percentage, breaks through the development framework of traditional Alloys mainly comprising 1 or 2 metal elements, has four effects of thermodynamic High Entropy effect, dynamic slow diffusion effect, lattice mismatch effect on crystal structure, performance cocktail effect and the like, can be designed according to requirements, and has the characteristics of High strength, High hardness, wear resistance, High temperature oxidation resistance, corrosion resistance and the like.
At present, most of reported high-entropy alloys are alloys with face-centered cubic (FCC) solid solution structure represented by CoCrFeMnNi, and Cu, Al and the like are added; the other is high-entropy alloy with high melting point single body-centered cubic (BCC) solid solution structure NbMoTaW and VNbMoTaW. The research aiming at the service working condition of the ship is blank, the existing high-entropy alloy material only focuses on single high strength and high toughness or single corrosion resistance research, an alloy material which integrates high strength and high toughness, seawater corrosion resistance and good antifouling performance matching is lacked, and the research on the exploratory property of the high-strength, high toughness, corrosion resistance and high entropy alloy is urgently needed to be developed to meet the application requirement of future ship equipment.
Disclosure of Invention
The invention provides a TiCuAlCrMoNi high-entropy alloy and a preparation method thereof, aiming at overcoming the defects that the existing high-entropy alloy does not have an antifouling function, and the marine titanium alloy is low in strength and easy to cause marine organism pollution.
The technical scheme adopted by the invention for solving the problems is as follows: a TiCuAlCrMoNi high entropy alloy is characterized in that: the composition of the high-entropy alloy is TiaCubAlcCrdMoeNifWherein a, b, c, d, e and f respectively represent the molar ratio of the corresponding elements, a is more than or equal to 0.3 and less than or equal to 1.5, b is more than or equal to 0.2 and less than or equal to 1.2, c is more than or equal to 0.2 and less than or equal to 1.5, d is more than or equal to 0.05 and less than or equal to 1.2, e is more than or equal to 0 and less than or equal to 1.2, and f is more than or equal to 0.05 and less.
A preparation method of a TiCuAlCrMoNi high-entropy alloy comprises the following steps:
placing titanium sponge, a Cu material, an Al material, a Cr material and a Ni material into a container, adding Mo and Al/Ti into the container in the form of Al-Mo/Ti-Mo intermediate alloy, and performing ultrasonic treatment for later use;
secondly, weighing the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are obtained in the first step and have equal molar weight or equal multiple molar ratio according to the components;
step three, placing the titanium sponge into one smelting pool of a water-cooled copper mold, and sequentially placing the rest materials weighed in the step two into the other smelting pool of the water-cooled copper mold according to the sequence of the melting points of the materials from bottom to top from low to high for standby; the materials are sequentially placed from bottom to top according to the sequence of the melting points of the materials from low to high, so that the smelting uniformity is ensured;
step four, pumping the vacuum chamber in the smelting furnaceVacuum to 5 × 10-3Pa, then filling argon to 0.01Pa, repeating the step for more than three times to clean the vacuum chamber;
and step five, respectively smelting the sponge titanium and the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material in the other smelting pool, sequentially casting to obtain an ingot A and an alloy ingot B, placing the ingot A and the alloy ingot B together, smelting for 3-5 times, turning the sample for 180 degrees after each smelting, smelting by the same method, and cooling along with the furnace to obtain the TiCuAlCrMoNi high-entropy alloy.
In the invention, the purities of the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material adopted in the first step are all more than 99.9%.
In the invention, the ultrasonic treatment method in the first step comprises the following steps: adding acetone into the container until all the materials are submerged, and ultrasonically cleaning for 15-20 min to remove oil stains and impurities attached to the surface; and then respectively placing the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are subjected to impurity removal into a container, adding absolute ethyl alcohol until all the materials are submerged, ultrasonically cleaning for 15-20 min, and then placing into an oven for drying to obtain the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are subjected to ultrasonic treatment.
In the invention, in the vacuum chamber in the fourth step, the purity of argon is more than or equal to 99.999 percent, the oxygen content is less than or equal to 1.5ppm, the nitrogen content is less than or equal to 50ppm, the carbon content is less than or equal to 4ppm, and the water content is less than or equal to 3 ppm.
In the fifth step, smelting is carried out by using a non-consumable vacuum arc smelting process, wherein sponge titanium is smelted for 1-2 min under the smelting current of 200-400A to obtain an alloy ingot A; and smelting the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material in the other smelting pool for 1-2 min under the current of 200-400A to obtain an alloy ingot B.
In the fifth step, the sponge titanium and Cu material, Al material, Cr material, Ni material and Al-Mo/Ti-Mo material in another smelting pool are smelted by adopting an electromagnetic suspension smelting process, the metal melt is suspended by means of Lorentz force formed by interaction between an electromagnetic field and induced current, and the metal is melted by means of induced current heating generated in a coil by an alternating electromagnetic field.
In the invention, the Mo element has higher melting point, and Al-Mo or Ti-Mo intermediate alloy is selected to replace pure metal during smelting. Titanium is a main element of the high-entropy alloy, a part or all of Ti is sponge titanium, the sponge titanium is generally sponge metal titanium produced by the existing metallothermic reduction method, the purity is not less than 99.8%, and the sponge titanium is loose, so that in order to prevent sponge titanium volatile matters from influencing the alloy performance during direct smelting, in the fifth step, the sponge titanium is smelted into an ingot, and then the ingot is fully fused with melts of other elements such as Cu, Al, Cr, Mo and Ni, and a high-entropy alloy ingot with low content of impurity elements, particularly O elements is obtained.
In the invention, Ti element is beneficial to improving the solid solution strengthening and lattice distortion characteristics of the alloy, Cu element has an antifouling function and can improve the antifouling characteristics of the alloy, and Cu is in a face-centered cubic crystal structure, and the Cu element can form a complete solid solution structure with the face-centered cubic structure at the temperature higher than 354 ℃ to improve the toughness of the alloy, so Ti and Cu are the preferred main elements for designing the alloy. Al has a face centered cubic crystal structure, and the crystal structure of the alloy is gradually converted from FCC to FCC + BCC along with the increase of the content of Al element, so the content of Al is not easy to be too high. Cr and Mo (refractory metals) can promote the conversion of the alloy from FCC to BCC, which is beneficial to improving the strength of the alloy, and meanwhile, Cr, Mo and Ti are common elements of the corrosion-resistant alloy, so that a compact oxide film is easily formed on the surface of the alloy to improve the corrosion resistance of the alloy.
Has the advantages that: 1. on the basis of Ti and Cu elements, alloying elements Al, Cr and Mo which are easy to improve the alloy strength and element Ni which is easy to improve the alloy toughness are selected as main elements of the alloy to prepare the TiCuAlCrMoNi high-entropy alloy system. The corrosion resistant alloy generated by Ti, Cr and Mo in the alloy is beneficial to enhancing the corrosion resistant performance of the alloy; the mol percentages of Cu, Cr, Mo and Ni are small, and the high-entropy alloy with low density can be obtained; meanwhile, Mo is a high-melting-point refractory metal element, can promote the conversion of the alloy from FCC to BCC, and is beneficial to improving the strength of the alloy.
2. The high-entropy alloy material with microhardness not lower than 550HV, seawater corrosion resistance and certain antifouling function is prepared by a non-consumable vacuum arc melting process or an electromagnetic suspension melting process, so that the defects of the traditional high-entropy alloy are overcome, and the application requirements of future ship materials are met. And controlling the smelting vacuum degree, the smelting current and the smelting times during alloy smelting to prepare the TiCuAlCrMoNi high-entropy alloy.
3. The high-entropy alloy prepared by the invention has the advantages of small density, high strength and hardness, excellent seawater corrosion resistance and certain antifouling function. Yield strength R of the developed alloyp0.2Not less than 1350MPa, tensile strength RmThe alloy has the advantages that the alloy has the advantages of being more than or equal to 1500MPa, the hardness of more than or equal to 550HV, the uniform corrosion rate of less than or equal to 0.001mm/a after being soaked in seawater at 60 ℃, the dissolution rate of copper ions is more than 10ppb, the alloy has excellent seawater corrosion resistance, has a certain antifouling function, overcomes the defects of poor comprehensive performance of the traditional high-entropy alloy and non-antifouling property of the existing titanium alloy, solves the key technologies of solid solution phase formation and phase transformation control in the high-entropy alloy, matching regulation and control of the mechanical property, the density and the corrosion resistance of the high-entropy alloy and the like, overcomes the defects of single high strength, corrosion resistance, poor comprehensive performance and non-antifouling property of the traditional high-entropy alloy, and has good application prospect in a marine pipeline.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein a, b, c, d, e and f represent the corresponding elements respectivelyThe molar ratio of a is more than or equal to 0.3 and less than or equal to 1.5, b is more than or equal to 0.2 and less than or equal to 1.2, c is more than or equal to 0.2 and less than or equal to 1.5, d is more than or equal to 0.05 and less than or equal to 1.2, e is more than or equal to 0 and less than or equal to 1.2, and f is more than or equal to 0.05.
Example 1
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein the molar ratio of any two elements is 1: 1.
a preparation method of a TiCuAlCrMoNi high-entropy alloy comprises the following steps:
firstly, ultrasonic treatment: placing titanium sponge, a Cu material, an Al material, a Cr material and a Ni material into a container, adding Mo, Al or Ti into the container in the form of Al-Mo/Ti-Mo intermediate alloy, adding acetone until all the materials are submerged, ultrasonically cleaning for 15-20 min, and removing oil stains and impurities attached to the surface; then placing the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are subjected to impurity removal into a container, adding absolute ethyl alcohol until all the materials are submerged, ultrasonically cleaning for 15-20 min, and placing the materials into an oven for drying to obtain the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are subjected to ultrasonic treatment;
II, preparing materials: weighing the components, and weighing the ultrasonically treated titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are obtained in the step one in an equimolar amount;
thirdly, smelting the high-entropy alloy: placing the titanium sponge into one smelting tank of a water-cooled copper mold, placing the ultrasonically treated Cu material, Al material, Cr material, Ni material and Al-Mo/Ti-Mo material which are weighed in the second step into the other smelting tank of the water-cooled copper mold, and placing the materials in sequence from bottom to top according to the melting points of the materials from low to high so as to ensure the smelting uniformity; wherein, Al, Cu, Ni, Cr, Al-Mo/Ti-Mo are placed from bottom to top in sequence;
② Water-cooled copper mold is positioned in the smelting furnace to form a closed spaceIs evacuated to 5 × 10-3Pa, then high purity argon gas was introduced to 0.01Pa, and the process was repeated three times or more to clean the vacuum chamber. Wherein, the purity of the high-purity argon is more than or equal to 99.999 percent, the oxygen content is less than or equal to 1.5ppm, the nitrogen content is less than or equal to 50ppm, the carbon content is less than or equal to 4ppm, and the water content is less than or equal to 3 ppm;
smelting sponge titanium for 1-2 min under the condition that the smelting current is 200-400A to obtain an ingot A, smelting the ultrasonically treated Cu material, Al material, Cr material, Ni material and Al-Mo/Ti-Mo material weighed in the second step for 1-2 min under the current of 200-400A to obtain an alloy ingot B, then placing the ingot A and the alloy ingot B together for smelting for 3-5 times, turning the sample 180 degrees after each smelting, then carrying out the same electric arc smelting, and cooling along with the furnace to obtain the TiCuAlCrMoNi high-entropy alloy.
The density of the TiCuAlCrMoNi high-entropy alloy obtained in the embodiment is 5.36g/cm3The microhardness is 782HV, the yield strength is 1495MPa, the tensile strength is 1960MPa, and the elongation is 13.6%. When the alloy is soaked in seawater at 60 ℃ for 60 days, the uniform corrosion rate of the alloy is 0.00025mm/a, the elution amount of copper ions is 372ppb, and the alloy has a certain antifouling effect.
Example 2
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein the mol percentages are that a is 1mol, b is 0.5mol, c is 1mol, d is 0.2mol, e is 0.3mol and f is 0.5 mol.
A preparation method of a TiCuAlCrMoNi high-entropy alloy comprises the following steps:
firstly, ultrasonic treatment: placing titanium sponge, a Cu material, an Al material, a Cr material and a Ni material into a container, adding Mo and Ti into the container in the form of Ti-Mo intermediate alloy, adding acetone until all the materials are submerged, and ultrasonically cleaning for 15-18 min to remove oil stains and impurities attached to the surface; and then placing the titanium sponge, the Cu material, the Al material, the Cr material, the Ti-Mo material and the Ni material after the impurities are removed into a container, adding absolute ethyl alcohol until all the materials are submerged, ultrasonically cleaning for 15-18 min, and placing the materials into an oven for drying to obtain the titanium sponge, the Cu material, the Al material, the Cr material, the Ti-Mo material and the Ni material after ultrasonic treatment.
II, preparing materials: weighing the components, and weighing the ultrasonically treated titanium sponge, the Cu material, the Al material, the Cr material, the Ti-Mo material and the Ni material which are obtained in the step one according to the equimolar amount of each element;
thirdly, smelting the high-entropy alloy: placing the titanium sponge into one smelting tank of a water-cooled copper mold, placing the ultrasonically treated Cu material, Al material, Cr material, Ti-Mo material and Ni material weighed in the second step into the other smelting tank of the water-cooled copper mold, and placing the materials from bottom to top according to the melting points of the materials from low to high so as to ensure the smelting uniformity; wherein Al, Cu, Ni, Cr and Ti-Mo are placed from bottom to top in sequence;
② Water-cooled copper mold is located in the smelting furnace, and the vacuum chamber in the smelting furnace is vacuumized to 5 × 10-3Pa, then high purity argon gas was introduced to 0.01Pa, and the process was repeated three times or more to clean the vacuum chamber. Wherein, the purity of the high-purity argon is more than or equal to 99.999 percent, the oxygen content is less than or equal to 1.5ppm, the nitrogen content is less than or equal to 50ppm, the carbon content is less than or equal to 4ppm, and the water content is less than or equal to 3 ppm;
③, firstly, smelting the sponge titanium for 1-2 min under the condition that the smelting current is 200-250A, secondly, smelting the ultrasonically treated Cu material, Al material, Cr material, Ti-Mo material and Ni material weighed in the second step for 1-2 min under the current of 200-250A to obtain an ingot, then placing the two materials together for smelting for 3-5 times, turning the sample 180 degrees after each smelting, then carrying out the same arc smelting, and cooling along with the furnace to obtain TiCu0.5AlCr0.2Mo0.3Ni0.5High entropy alloy.
TiCu obtained in this example0.5AlCr0.2Mo0.3Ni0.5High entropy alloy with density of 5.12g/cm3Microhardness of 748HV, yield strength of 1470MPa, tensile strength of 1952MPa, ductilityThe elongation was 15.1%. When the alloy is soaked in seawater at 60 ℃ for 60 days, the uniform corrosion rate of the alloy is 0.00032mm/a, the elution amount of copper ions is 322ppb, and the alloy has a certain antifouling effect.
Example 3
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein the mol percentages are that a is 0.9mol, b is 0.6mol, c is 0.2mol, d is 0.5mol, e is 0mol, and f is 0.05 mol.
A preparation method of a TiCuAlCrNi high-entropy alloy comprises the following steps:
placing titanium sponge, a Cu material, an Al material, a Cr material and a Ni material into a container, adding acetone until all the materials are submerged, and ultrasonically cleaning for 15-20 min to remove oil stains and impurities attached to the surface; then respectively placing the titanium sponge, the Cu material, the Al material, the Cr material and the Ni material after the impurities are removed into a container, adding absolute ethyl alcohol until all the materials are submerged, ultrasonically cleaning for 15-20 min, and then placing the materials into an oven for drying to obtain the titanium sponge, the Cu material, the Al material, the Cr material and the Ni material after ultrasonic treatment;
secondly, weighing the titanium sponge, the Cu material, the Al material, the Cr material and the Ni material which are obtained in the first step and have equal molar weight or a certain molar ratio according to the components;
thirdly, placing the titanium sponge into one smelting tank of a water-cooled copper mold, and sequentially placing the Cu material, the Al material, the Cr material and the Ni material weighed in the second step into the other smelting tank of the water-cooled copper mold from bottom to top according to the melting points of the materials, so as to ensure the smelting uniformity; wherein Al, Cu, Ni and Cr are placed from bottom to top in sequence;
step four, vacuumizing the vacuum chamber in the smelting furnace to 5 × 10-3Pa, then filling argon to 0.01Pa, repeating the step for more than three times to clean the vacuum chamber; wherein,the purity of the argon is more than or equal to 99.999 percent, the oxygen content is less than or equal to 1.5ppm, the nitrogen content is less than or equal to 50ppm, the carbon content is less than or equal to 4ppm, and the water content is less than or equal to 3 ppm.
Step five, smelting the titanium sponge for 1-2 min under the smelting current of 250-400A by utilizing a non-consumable vacuum arc smelting process, and casting to obtain an ingot A; smelting a Cu material, an Al material, a Cr material and a Ni material in the other smelting pool for 1-2 min under the smelting current of 250-400A, casting to obtain an alloy ingot B, smelting the ingot A and the alloy ingot B together according to the method for 4-5 times, turning over a sample for 180 degrees after each smelting, smelting by the same method, cooling along with the furnace to obtain Ti0.9Cu0.6Al0.2Cr0.5Ni0.05High entropy alloy.
Ti obtained in this example0.9Cu0.6Al0.2Cr0.5Ni0.05High entropy alloy with density of 4.98g/cm3The microhardness is 802HV, the yield strength is 1398MPa, the tensile strength is 1915MPa, and the elongation is 17.9%. When the alloy is soaked in seawater at 60 ℃ for 60 days, the uniform corrosion rate of the alloy is 0.00045mm/a, the elution amount of copper ions is 271ppb, and the alloy has a certain antifouling effect.
Example 4
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein the mole percentages are that a is 0.9mol, b is 0.6mol, c is 1.2mol, d is 0.7mol, e is 0mol, and f is 0.3 mol.
A method for preparing TiCuAlCrNi high entropy alloy, the step one to the step four of the preparation method are the same as embodiment 1, in embodiment 4, an electromagnetic suspension smelting process is adopted to smelt sponge titanium and Cu material, Al material, Cr material and Ni material in another smelting pool, a metal melt is suspended by Lorentz force formed by interaction between an electromagnetic field and induced current, and the induced current generated in a coil by an alternating electromagnetic field is used for heating and smelting the metal; then will obtainThe ingot A and the alloy ingot B are placed together and smelted for 3-5 times according to an electromagnetic suspension smelting process, and after the sample is turned over for 180 degrees after each smelting, the ingot is smelted by the same method, so that the ingot components are more uniform. Cooling with the furnace to obtain Ti0.9Cu0.6Al1.2Cr0.7Ni0.3High entropy alloy.
Ti obtained in this example0.9Cu0.6Al1.2Cr0.7Ni0.3High entropy alloy with density of 5.02g/cm3The microhardness is 817HV, the yield strength is 1410MPa, the tensile strength is 1950MPa, and the elongation is 16.0%. When the alloy is soaked in seawater at 60 ℃ for 60 days, the uniform corrosion rate of the alloy is 0.00042mm/a, the elution amount of copper ions is 230ppb, and the alloy has a certain antifouling effect.
In the invention, the electromagnetic suspension smelting process comprises the following steps: suspending the molten alloy solution by using an electromagnetic force suspension technology, wherein high-frequency alternating current is conducted in a coil, and the smelting current is 80-120A; a high-frequency alternating magnetic field is communicated around the coil, an induced vortex is generated in the material, and the suspension force and the self weight of the material reach a force balance state.
Example 5
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein the mole percentages are a is 0.3mol, b is 0.2mol, c is 1.5mol, d is 1.2mol, e is 0.7mol and f is 0.05 mol. The preparation method is the same as that in example 3, wherein the adopted raw materials are sponge titanium, a Cu material, an Al material, a Cr material, an Al-Mo material and a Ni material, and Ti is prepared0.3Cu0.2Al1.5Cr1.2Mo0.7Ni0.05High entropy alloy.
Ti obtained in this example0.3Cu0.2Al1.5Cr1.2Mo0.7Ni0.05High entropy alloy with density of 5.49g/cm3Microhardness of 716HV, yield strength of 1398MPa, tensile strength of 1850MPa and elongation of 13.5 percent. When the alloy is soaked in seawater at 60 ℃ for 60 days, the uniform corrosion rate of the alloy is 0.00052mm/a, the elution amount of copper ions is 72ppb, and the alloy has a certain antifouling effect.
Example 6
A high-entropy TiCuAlCrMoNi alloy contains TiaCubAlcCrdMoeNifWherein the mole percentages are that a is 1.5mol, b is 1.2mol, c is 0.8mol, d is 0.05mol, e is 1.2mol, and f is 1.2 mol. The preparation method is the same as that of example 1, wherein the adopted raw materials are sponge titanium, a Cu material, an Al material, a Cr material, an Al-Mo material and a Ni material, and Ti is prepared1.5Cu1.2Al0.8Cr0.05Mo1.2Ni1.2High entropy alloy.
Ti obtained in this example1.5Cu1.2Al0.8Cr0.05Mo1.2Ni1.2High entropy alloy with density of 4.91g/cm3The microhardness is 730HV, the yield strength is 1435MPa, the tensile strength is 1862MPa, and the elongation is 12.1%. When the alloy is soaked in seawater at 60 ℃ for 60 days, the uniform corrosion rate of the alloy is 0.00015mm/a, the copper ion elution amount is 542ppb, and the alloy has a certain antifouling effect.
The TiCuAlCrMoNi high-entropy alloy prepared by the method has the yield strength of not less than 1350MPa, the tensile strength of not less than 1500MPa and the hardness of not less than 550 HV; the high-entropy alloy has excellent seawater corrosion resistance and a certain antifouling function, overcomes the defect that the traditional high-entropy alloy only focuses on single high strength or single corrosion resistance, obtains an alloy material with well-matched strength, hardness, corrosion resistance and antifouling performance, fills the blank of the research of the high-entropy alloy in the field of ships, expands a new application direction, and lays a theoretical foundation for the feasibility of the engineering application of the high-entropy alloy in the field of ships in the future.
Claims (7)
1. A TiCuAlCrMoNi high entropy alloy is characterized in that: the composition of the high-entropy alloy is TiaCubAlcCrdMoeNifWherein a, b, c, d, e and f respectively represent the molar ratio of the corresponding elements, a is more than or equal to 0.3 and less than or equal to 1.5, b is more than or equal to 0.2 and less than or equal to 1.2, c is more than or equal to 0.2 and less than or equal to 1.5, d is more than or equal to 0.05 and less than or equal to 1.2, e is more than or equal to 0 and less than or equal to 1.2, and f is more than or equal to 0.05 and less.
2. The method for preparing the TiCuAlCrMoNi high-entropy alloy of claim 1, comprising the following steps:
placing titanium sponge, a Cu material, an Al material, a Cr material and a Ni material into a container, adding Mo and Al/Ti into the container in the form of Al-Mo/Ti-Mo intermediate alloy, and performing ultrasonic treatment for later use;
secondly, weighing the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are obtained in the first step and have equal molar weight or equal multiple molar ratio according to the components;
step three, placing the titanium sponge into one smelting pool of a water-cooled copper mold, and sequentially placing the rest materials weighed in the step two into the other smelting pool of the water-cooled copper mold according to the sequence of the melting points of the materials from bottom to top from low to high for standby;
step four, vacuumizing the vacuum chamber in the smelting furnace to 5 × 10-3Pa, then filling argon to 0.01Pa, repeating the step for more than three times to clean the vacuum chamber;
and step five, respectively smelting the sponge titanium and the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material in the other smelting pool, sequentially casting to obtain an ingot A and an alloy ingot B, placing the ingot A and the alloy ingot B together, smelting for 3-5 times, turning the sample for 180 degrees after each smelting, smelting by the same method, and cooling along with the furnace to obtain the TiCuAlCrMoNi high-entropy alloy.
3. The method for preparing the TiCuAlCrMoNi high-entropy alloy as claimed in claim 2, wherein the method comprises the following steps: the mass percentage content, namely the purity, of the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material adopted in the first step is more than 99.9 percent.
4. The method for preparing the TiCuAlCrMoNi high-entropy alloy as claimed in claim 2, wherein the method comprises the following steps: the ultrasonic treatment method in the first step comprises the following steps: adding acetone into the container until all the materials are submerged, and ultrasonically cleaning for 15-20 min to remove oil stains and impurities attached to the surface; and then respectively placing the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are subjected to impurity removal into a container, adding absolute ethyl alcohol until all the materials are submerged, ultrasonically cleaning for 15-20 min, and then placing into an oven for drying to obtain the titanium sponge, the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material which are subjected to ultrasonic treatment.
5. The method for preparing the TiCuAlCrMoNi high-entropy alloy as claimed in claim 2, wherein the method comprises the following steps: in the vacuum chamber in the fourth step, the purity of argon is more than or equal to 99.999 percent, the oxygen content is less than or equal to 1.5ppm, the nitrogen content is less than or equal to 50ppm, the carbon content is less than or equal to 4ppm, and the water content is less than or equal to 3 ppm.
6. The method for preparing the TiCuAlCrMoNi high-entropy alloy as claimed in claim 2, wherein the method comprises the following steps: step five, smelting by using a non-consumable vacuum arc smelting process, wherein sponge titanium is smelted for 1-2 min under a smelting current of 200-400A to obtain an alloy ingot A; and smelting the Cu material, the Al material, the Cr material, the Ni material and the Al-Mo/Ti-Mo material in the other smelting pool for 1-2 min under the current of 200-400A to obtain an alloy ingot B.
7. The method for preparing the TiCuAlCrMoNi high-entropy alloy as claimed in claim 2, wherein the method comprises the following steps: and fifthly, smelting the sponge titanium and Cu materials, Al materials, Cr materials, Ni materials and Al-Mo/Ti-Mo materials in another smelting pool by adopting an electromagnetic suspension smelting process, suspending the metal melt by virtue of Lorentz force formed by interaction between an electromagnetic field and induced current, and heating and smelting the metal by utilizing the induced current generated in the coil by utilizing an alternating electromagnetic field.
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