High-wear-resistance dual-phase metal compound and preparation method thereof
Technical Field
The invention belongs to the field of preparation of inorganic metal compounds, and particularly relates to a high-wear-resistance two-phase metal compound AlxCeyCuFeNiMnpOqZr and a preparation method thereof.
Background
The metal compound (or called inorganic metal compound) is formed by combining a plurality of elements in the compound according to a certain stoichiometric ratio, the crystal structure of the formed metal compound is completely different from the crystal structure types of the constituent elements, the crystal structure of the metal compound is generally complex, the typical characteristic is that the crystal structure type of the metal compound is different from that of any constituent element, and the composition can be represented by a chemical formula rather than a composition. Metal compounds are important constituent phases of many alloys. The presence of metal compounds in conventional alloys generally increases the hardness and wear resistance of the alloy, but decreases the ductility and toughness. At the beginning of the 20 th century, the Ye project group and the Cantor project group in taiwan in the united kingdom each independently reported a novel multi-principal-element high-entropy alloy, which is significantly different from the conventional theory that hard and brittle intermetallic compounds are formed. Although the reported novel multi-principal element high-entropy alloys tend to form simple crystal structures, such as: face Centered Cubic (FCC), Body Centered Cubic (BCC), Hexagonal Close Packed (HCP), Simple Cubic (SC), etc.; but is distinguished from the space group or lattice constant of the Face Centered Cubic (FCC) metals (e.g., aluminum, copper, gold, silver, nickel, etc.), the Body Centered Cubic (BCC) metals (e.g., potassium, molybdenum, tungsten, etc.), the Hexagonal Close Packed (HCP) metals (e.g., magnesium, zinc, beryllium, etc.), the Simple Cubic (SC) metals (e.g., polonium is the only element with a simple cubic structure), and the distinction is made between the types of conventional alloys, i.e., between aluminum and copper belonging to the face centered cubic phase structure, and the distinction is made based on the crystal structure and the lattice constant of the conventional alloys and the high entropy alloy types. Formally based on the design concept of the novel metal compound, a small amount of non-metal elements are introduced to modify the metal compound, and the high-wear-resistance two-phase Al is designed and preparedxCeyCuFeNiMnpOqA Zr metal compound. The invention relates to high-wear-resistance biphase AlxCeyCuFeNiMnpOqThe Zr metal compound belongs to the invention patent of the compound with a typical novel crystal structure, but not the composition invention patent, and improves the hardness and the strength at the same timePlasticity and toughness. Therefore, the novel high-wear-resistance dual-phase metal compound with strong hardness and plasticity and toughness is designed and prepared, and has important practical significance and market prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-wear-resistance two-phase metal compound AlxCeyCuFeNiMnpOqZr and a preparation method thereof.
Al provided by the inventionxCeyCuFeNiMnpOqThe multi-principal-element alloy prepared by the vacuum melting method is a two-phase metal compound structure consisting of two simple cubic phases (SC1 and SC2), and the molecular formula of the multi-principal-element alloy is AlxCeyCuFeNiMnpOqZr; the two-phase proportion can be regulated and controlled according to the performance requirement; the prepared alloy has high density, high hardness and high wear resistance.
The technical scheme for realizing the invention is as follows: al (Al)xCeyCuFeNiMnpOqThe preparation method of the Zr metal compound is characterized by comprising the following specific steps:
(1) according to the chemical formula AlxCeyCuFeNiMnpOqZr, wherein x is more than or equal to 0.1 and less than or equal to 1.3; y is more than or equal to 0.1 and less than or equal to 1; p is more than or equal to 0.1 and less than or equal to 1.3; q is more than or equal to 0.1 and less than or equal to 0.5; 0.02 ≤ x/(x + y + p + q +4)<0.25;0.01≤y/(x+y+p+q+4)<0.18;0.02≤p/(x+y+p+q+4)<0.25;0.01≤q/(x+y+p+q+4)<0.10; respectively weighing the required pure metal powder and adding a proper amount of cerium dioxide according to the proportion of oxygen elements; placing the raw material powder into a ball milling tank, adding a stainless steel ball, and sealing the ball milling tank under a protective gas environment;
(2) placing the ball milling tank sealed in the step (1) on a planetary ball mill for mixing;
(3) putting the fully mixed powder in the step (2) into a graphite die, and pressing the fully mixed powder into a block at 600 ℃ and 35MPa in a discharge plasma sintering furnace;
(4) putting the block in the step (3) into a vacuum smelting furnace, and when the vacuum degree reaches 1 multiplied by 10-3After Pa, argon is filled in, andvacuumizing, repeatedly vacuumizing and filling argon for 3 times, then starting to smelt, repeatedly smelting for 3 times to ensure the uniformity of the material, carrying out vacuum suction casting in a water-cooled copper mold, and taking out a sample to obtain the target compound.
In the step (1), the purity of the metal powder is higher than 99.5%, and the purity of the cerium dioxide is higher than 99.9%.
And (2) the protective gas in the step (1) is argon or nitrogen.
And (3) mixing in the step (2) at the rotating speed of 30-100 rpm for 0.5-6 h.
The smelting process parameters in the step (4) are as follows: the current is 250-400A, and the action time is 30-120 s.
The invention has the beneficial effects that: the metal compound prepared by the method has the same proportioning components with the metal elements of the raw materials, and the phase structure of the metal compound is a two-phase metal compound structure consisting of two simple cubic phases; the two-phase proportion can be regulated and controlled according to the performance requirement; the prepared metal compound has high density, high hardness and high wear resistance; low cost and wide application range.
Drawings
FIG. 1 shows a high wear-resistant two-phase metal compound Al provided by the inventionxCeyCuFeNiMnpOqA process flow diagram of a preparation method of Zr;
FIG. 2 is an X-ray diffraction pattern of the metal compound prepared in example 1.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
Example 1
According to the chemical formula of AlCo0.1CuFeNiMnO0.1Respectively weighing 0.40mol of aluminum powder, copper powder, iron powder, nickel powder, manganese powder and zirconium powder, 0.02mol of cerium powder and 0.02mol of cerium dioxide by using Zr, wherein the purity of each metal powder is higher than 99.5 percent, and the purity of the cerium dioxide is higher than 99.9 percent; placing the raw material powder into a ball milling tank, adding a stainless steel ball, and then sealing the ball milling tank under an argon environment; placing the sealed ball milling tank in a planetary ballMixing materials on a mill at the rotating speed of 30rpm for 6 hours; putting the fully mixed powder into a graphite die, and pressing the fully mixed powder into a block at 600 ℃ and 35MPa in a discharge plasma sintering furnace; placing the block in a vacuum melting furnace, and when the vacuum degree reaches 1 × 10-3And Pa, introducing argon, vacuumizing again, repeatedly vacuumizing and introducing argon for 3 times, then starting smelting, wherein the current is 400A, the action time is 30s, repeatedly smelting for 3 times to ensure the uniformity of the material, performing vacuum suction casting in a water-cooling copper mold, and taking out a sample to obtain the target compound.
Example 2
Is represented by the chemical formula Al1.3Ce0.1CuFeNiMn0.1O0.1Respectively weighing 0.52mol of aluminum powder, 0.40mol of copper powder, iron powder, nickel powder and zirconium powder, 0.02mol of cerium dioxide and 0.04mol of manganese powder by using Zr, wherein the purity of each metal powder is higher than 99.5 percent, and the purity of the cerium dioxide is higher than 99.9 percent; placing the raw material powder into a ball milling tank, adding a stainless steel ball, and then sealing the ball milling tank under an argon environment; placing the sealed ball milling tank on a planetary ball mill for mixing materials, wherein the rotating speed is 50rpm, and the time is 3 hours; putting the fully mixed powder into a graphite die, and pressing the fully mixed powder into a block at 600 ℃ and 35MPa in a discharge plasma sintering furnace; placing the block in a vacuum melting furnace, and when the vacuum degree reaches 1 × 10-3And Pa, introducing argon, vacuumizing again, repeatedly vacuumizing and introducing argon for 3 times, then starting smelting, wherein the current is 350A, the action time is 60s, repeatedly smelting for 3 times to ensure the uniformity of the material, performing vacuum suction casting in a water-cooling copper mold, and taking out a sample to obtain the target compound.
Example 3
Is represented by the chemical formula Al0.1Ce0.1CuFeNiMn1.3O0.1Respectively weighing 0.04mol of aluminum powder, 0.40mol of copper powder, iron powder, nickel powder and zirconium powder, 0.02mol of cerium dioxide and 0.52mol of manganese powder by using Zr, wherein the purity of each metal powder is higher than 99.5 percent, and the purity of the cerium dioxide is higher than 99.9 percent; placing the raw material powder into a ball milling tank, adding a stainless steel ball, and then sealing the ball milling tank under an argon environment; ball milling the sealed ballThe pot is placed on a planetary ball mill for mixing materials, the rotating speed is 100rpm, and the time is 0.5 h; putting the fully mixed powder into a graphite die, and pressing the fully mixed powder into a block at 600 ℃ and 35MPa in a discharge plasma sintering furnace; placing the block in a vacuum melting furnace, and when the vacuum degree reaches 1 × 10-3And Pa, introducing argon, vacuumizing again, repeatedly vacuumizing and introducing argon for 3 times, then starting smelting, wherein the current is 250A, the action time is 120s, repeatedly smelting for 3 times to ensure the uniformity of the material, performing vacuum suction casting in a water-cooling copper mold, and taking out a sample to obtain the target compound.
Example 4
Is represented by the chemical formula Al0.5CeCuFeNiMn0.5O0.1Respectively weighing 0.20mol of aluminum powder and manganese powder, 0.40mol of copper powder, iron powder, nickel powder and zirconium powder, 0.38mol of cerium powder and 0.02mol of cerium dioxide by using Zr, wherein the purity of each metal powder is higher than 99.5 percent, and the purity of the cerium dioxide is higher than 99.9 percent; placing the raw material powder into a ball milling tank, adding a stainless steel ball, and sealing the ball milling tank in a nitrogen environment; placing the sealed ball milling tank on a planetary ball mill for mixing materials, wherein the rotating speed is 100rpm, and the time is 0.5 h; putting the fully mixed powder into a graphite die, and pressing the fully mixed powder into a block at 600 ℃ and 35MPa in a discharge plasma sintering furnace; placing the block in a vacuum melting furnace, and when the vacuum degree reaches 1 × 10-3And Pa, introducing argon, vacuumizing again, repeatedly vacuumizing and introducing argon for 3 times, then starting smelting, wherein the current is 250A, the action time is 120s, repeatedly smelting for 3 times to ensure the uniformity of the material, performing vacuum suction casting in a water-cooling copper mold, and taking out a sample to obtain the target compound.
Example 5
Is represented by the chemical formula Al0.5Ce0.3CuFeNiMn0.5O0.5Respectively weighing 0.20mol of aluminum powder and manganese powder, 0.40mol of copper powder, iron powder, nickel powder and zirconium powder, 0.02mol of cerium powder and 0.10mol of cerium dioxide by using Zr, wherein the purity of each metal powder is higher than 99.5 percent, and the purity of the cerium dioxide is higher than 99.9 percent; placing the raw material powder into a ball milling tank, adding a stainless steel ball, and sealing the ball milling tank in a nitrogen environment; placing the sealed ball milling tankMixing materials on a planetary ball mill at the rotating speed of 50rpm for 3 hours; putting the fully mixed powder into a graphite die, and pressing the fully mixed powder into a block at 600 ℃ and 35MPa in a discharge plasma sintering furnace; placing the block in a vacuum melting furnace, and when the vacuum degree reaches 1 × 10-3And Pa, introducing argon, vacuumizing again, repeatedly vacuumizing and introducing argon for 3 times, then starting smelting, wherein the current is 350A, the action time is 60s, repeatedly smelting for 3 times to ensure the uniformity of the material, performing vacuum suction casting in a water-cooling copper mold, and taking out a sample to obtain the target compound.