CN104451351A - Method for improving toughness of boracic high-entropy alloy by adding rare earth - Google Patents
Method for improving toughness of boracic high-entropy alloy by adding rare earth Download PDFInfo
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- CN104451351A CN104451351A CN201410820809.9A CN201410820809A CN104451351A CN 104451351 A CN104451351 A CN 104451351A CN 201410820809 A CN201410820809 A CN 201410820809A CN 104451351 A CN104451351 A CN 104451351A
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Abstract
The invention discloses a method for improving the toughness of a boracic high-entropy alloy by adding rare earth, belonging to the technical field of alloy materials. According to the component design idea of the invention, a boron element with the mole fraction of 0.1-8% is added into a high-entropy alloy consisting of five or more than five elements, and meanwhile 0.1-4% of a rare earth element such as Y or Ce is added together. Due to addition of the rare earth elements, the gap solid solution reinforcement effect of the small atom boron element in the high-entropy alloy is improved, and the separation content, the morphology and the distribution of rigid boride hard phase are improved, so that the strength and the toughness of the boracic high-entropy alloy are synchronously improved.
Description
Technical field
The invention belongs to technical field of alloy, be specifically related to a kind of rare earth that adds and improve boracic high-entropy alloy medium and small atomic boron gap solid solution strengthening effect, improve boride and separate out form and distribution, the synchronous method improving boracic high-entropy alloy obdurability.
Background technology
High-entropy alloy is one of focus of new structural metallic materials research in recent years, and its primary alloy constituent is configured with equimolar ratio or nearly equimolar ratio by 5 to 11 kinds of principal elements, can have good hardness, intensity, corrosion-resistant, resistance to oxidation and high-temperature heat-resistance performance concurrently.The main enhancement method that high-entropy alloy has been reported, generally by improving the thick atom alloying element contents such as Al, Ti, Mo to increase the lattice distortion of over-saturation substitutional solid solution, promotes solid solution strengthening effect.From atomic structure, solution strengthening theory thinks that the distortion that displaced type solid solution atom causes in matrix lattice is mostly spherically symmetric, and the interpolation of interstitial atom can make lattice produce asymmetrical distortion, there are some researches show the solid solution strengthening effect of interstitial atom apparently higher than substitutional solid solution.But the interstitial compound that both can be made to be formed due to combination strong between nonmetal and metallic element has high thermodynamics TiFe_xM_y alloy, add in high-entropy alloy after little atomic boron element very easily causes alloy graining and separate out brittle borides thick in a large number, reduce the toughness of solid solution strengthening effect and alloy.Therefore, improve the solid solution strengthening effect of nonmetal little atomic boron in high-entropy alloy, improve precipitation content and the form of the thick boride of fragility, become synchronous and improve boracic high-entropy alloy obdurability technology in the urgent need to address.
Summary of the invention
For overcoming the deficiencies in the prior art, the present invention proposes and a kind ofly add the method that a small amount of rare-earth yttrium or Ce elements improve little atomic boron strengthening effect in high-entropy alloy, to improving the precipitation content of brittle borides hard phase, form and distribution, thus synchronous intensity and the toughness improving boracic high-entropy alloy.
In order to realize above technical purpose, the present invention is achieved by the following technical programs.
The present invention is a kind of adds the method that rare earth improves boracic high-entropy alloy obdurability, specifically: combine in high-entropy alloy elementary composition more than 5 kinds or 5 kinds simultaneously and add boron and rare earth element; In described high-entropy alloy composition, often kind of constituent content accounts for 2 ~ 35% of alloy total mole number respectively; The boron content of described interpolation accounts for 0.1 ~ 8% of alloy total mole number; The rare earth element of described interpolation is yttrium or cerium, and it accounts for 0.1 ~ 4% of alloy total mole number.
The principles of science of the present invention and effect:
Contrast with the identical component boracic high-entropy alloy not containing rare earth element, rare earth element can reduce precipitation content and the size of thick boride in boracic high-entropy alloy, improve boride distributional pattern, be conducive to improving the gap solid solubility of boron in high-entropy alloy solid solution matrix, thus improve the gap solid solution of boron in high-entropy alloy and second-phase strength effect, avoid toughness to reduce rapidly while improving high-entropy alloy hardness.In addition, rare earth element can also play purification crystal boundary similar in conventional alloys, the effect of crystal grain thinning.
Proposition of the present invention solves the not easily solid solution in high-entropy alloy of nonmetal boron, often with the problem that thick brittle borides form is separated out, thus can promote the highly malleablized effect of boracic high-entropy alloy, improve high-entropy alloy comprehensive mechanical property, and use wide general.
Accompanying drawing explanation
Fig. 1 is that in arc melting iron-cobalt-nickel chromium aluminium 8% boron block high-entropy alloy tissue, boride separates out shape appearance figure.
Fig. 2 is that in arc melting iron-cobalt-nickel chromium aluminium 8% boron 4% yttrium block high-entropy alloy tissue, boride separates out shape appearance figure.
Fig. 3 is that in laser melting coating iron-cobalt-nickel chromium-copper 2% boron high-entropy alloy coating, boride separates out shape appearance figure.
Fig. 4 is that in laser melting coating iron-cobalt-nickel chromium-copper 2% boron 1% yttrium high-entropy alloy coating, boride separates out shape appearance figure.
Embodiment
Prepare more than 5 kinds elementary composition high-entropy alloys by the requirement of Composition Design, then add boron and the rare earth element of desired content.Its purity of sample raw material chosen is not less than 99%, intercepts appropriate raw material, then mixed by obtained raw material from mother metal.Adopt electric-heating-wire-heating method subsequently, induction heating, the block materials technologies of preparing such as mechanical alloying method, powder metallurgic method, arc melting method, or the high-entropy alloy coating of adding boron and rare earth element is combined in the preparation of the coat preparing technology such as laser melting coating, plasma spraying.Displaing micro tissue topography is adopted to observe the form of boride precipitation on melted sample, utilize Vickers hardness tester test sample hardness simultaneously, experiment power is 10Kg, due to the crackle that the fragility that material is different will cause indentation hardness tip to form different lengths, the fragility of the crack length change comparative material formed by various sample impression tip.Below will prepare boracic high-entropy alloy coating by embodiment 1 arc melting block boracic high-entropy alloy and embodiment 2 laser melting coating and the concrete implementation result of the present invention will be described.
Embodiment 1
Get the Determination of multiple metal elements such as Fe, Co, Ni, Cr, Cu, Mn, Mo, and add the little atomic boron element of different content and rare earth element yttrium or cerium in the alloy, configuration high-entropy alloy composition label 1 ~ 3 group totally 9 compositions respectively, add boron, rare earth element to the impact of high-entropy alloy hardness and fragility for comparing to combine, constitution number is as shown in table 1.Be placed in the water cooled copper mould of vacuum arc furnace melting stove by the one-tenth that each group configuration is good, then cover bell, first vacuum suction is to pouring pure argon after about 0.01 normal atmosphere, then starts melting after repeatedly pumping and reboot operation 1 ~ 2 time.After each smelting solidification completes, the alloy turn-over in copper mold is dissolved for electric arc again, so repeatedly for several times until all alloy Homogeneous phase mixing positions.Sample carries out Mechanics Performance Testing after having prepared, and the test results such as Vickers' hardness and the most advanced and sophisticated crack length of impression are in table 1.As can be seen from the table, although three compositions divide in high-entropy alloys can play as only added boron the effect significantly improving hardness, the crack length that impression tip is formed obviously increases, and shows the interpolation of a small amount of boron unfavorable to the toughness of high-entropy alloy.And add a small amount of rare earth element in boracic high-entropy alloy after, sample not only hardness significantly increases simultaneously, and most advanced and sophisticated crack growth length obviously reduces, close to the contrast composition sample not adding boron.Result shows to combine interpolation rare earth element in boracic high-entropy alloy, is conducive to synchronously improving boracic high-entropy alloy obdurability.Fig. 1 and Fig. 2 is that the first composition divides No. 2 and No. 3 sample tissue comparing results, can find out and occur a large amount of block boride precipitated phase grown with facet crystal type in tissue after adding 8% boron in iron-cobalt-nickel Ohmax, and the precipitation content of boride obviously reduces in organizing add 4% rare-earth yttrium in same amount boracic high-entropy alloy after, the refinement of boride precipitate size, illustrate that the interpolation of rare-earth yttrium is to the gap solid solubility improving the little atomic boron of boracic high-entropy alloy, improving boride precipitation form has obvious effect.
The most advanced and sophisticated crack length of the component of table 1 arc melting boracic high-entropy alloy, hardness value and impression
Embodiment 2
Get the Determination of multiple metal elements powder such as Fe, Co, Ni, Cr, Cu, Mn, Ti, Mo, and add little atomic boron and the powder such as rare earth element yttrium, cerium of different content in the alloy, powder diameter 50 ~ 300 μm.According to the configuration of composition shown in table 2 boracic high-entropy alloy coated component respectively label 4 ~ 6 groups totally 9 compositions add boron, rare earth element to the impact of laser melting coating high-entropy alloy coating hardness and fragility for comparing to combine.Laser melting and coating process measure: first the body materials such as iron-based or Ni-based or cobalt-based are carried out the pre-treatment such as surface derusting, decontamination, preheating; Subsequently with semi-conductor or CO
2laser apparatus adopts reverse synchronous mode or coaxial-type automatic powder feeding system, what cladding had configured the be numbered high-entropy alloy powder of 4 ~ 6 groups; And the protection of inert gas such as synchronous argon gas or nitrogen are carried out to Laser Cladding Treatment region simultaneously; The laser cladding technological parameter adopted is: laser power 1 ~ 5kW, laser scanning speed 100 ~ 500mm/min, laser spot diameter 2 ~ 6mm, laser multi-pass overlapping rate 20 ~ 60%.Utilize Vickers hardness tester to measure the hardness of coating subsequently, and judge the impact of rare earth element on coating failure toughness according to the crack length that Vickers' hardness impression tip is formed.List different control group hardness in table 2 and become length with flaw shape, can find out that result and the arc melting block sample result of laser melting coating boracic high-entropy alloy coating are similar, combine the fragility of adding rare earth element and being conducive to reducing boracic high-entropy alloy, synchronous raising high-entropy alloy obdurability.Fig. 3 and Fig. 4 is the 4th composition point No. 11 and No. 12 sample tissue comparing results, can find out and occur a large amount of strip boride precipitated phase grown with facet crystal type in tissue after adding 2% boron in iron-cobalt-nickel chromium-copper coating, and elongated boride precipitated phase is not obvious visible in organizing after combining interpolation 1% rare-earth yttrium, the most advanced and sophisticated crackle of impression shortens, the corresponding raising of obdurability.Illustrate that the interpolation of rare earth element is to the gap solid solubility improving the medium and small atomic boron of laser melting coating boracic high-entropy alloy coating, improve boride and separate out form, the synchronous high-entropy alloy coating obdurability that improves has obvious effect.
The most advanced and sophisticated crack length of the component of table 2 laser melting coating boracic high-entropy alloy coating, hardness value and impression
Claims (1)
1. add the method that rare earth improves boracic high-entropy alloy obdurability, it is characterized in that, combine in high-entropy alloy elementary composition more than 5 kinds or 5 kinds simultaneously and add boron and rare earth element;
In described high-entropy alloy composition, often kind of constituent content accounts for 2 ~ 35% of alloy total mole number respectively;
The boron content of described interpolation accounts for 0.1 ~ 8% of alloy total mole number;
The rare earth element of described interpolation is yttrium or cerium, and it accounts for 0.1 ~ 4% of alloy total mole number.
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| CN110310793A (en) * | 2019-06-28 | 2019-10-08 | 江苏大学 | A kind of Hard Magnetic high-entropy alloy and preparation method thereof |
| CN110449580A (en) * | 2019-07-26 | 2019-11-15 | 广东工业大学 | A kind of powder metallurgy high-strength tenacity boracic high entropy alloy material and its preparation method and application |
| CN111235458A (en) * | 2020-02-28 | 2020-06-05 | 江苏大学 | Boron-containing rare earth-containing high-entropy alloy and magnetic field treatment method thereof |
| CN111394721A (en) * | 2020-05-29 | 2020-07-10 | 济南大学 | High-entropy alloy powder mixture, coating and coating preparation method |
| WO2020155283A1 (en) * | 2019-01-28 | 2020-08-06 | 广东工业大学 | High-entropy alloy boride ceramic, and preparation method therefor and application thereof |
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