CN107142410B - CrMoNbTiZr high entropy alloy materials and preparation method thereof - Google Patents
CrMoNbTiZr high entropy alloy materials and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high entropy alloy material and its technologies of preparing.High entropy alloy material ingredient is CrMoNbTiZr, wherein Cr:Mo:Nb:Ti:The molar ratio of Zr is followed successively by：1:1:1:1:1.Its preparation process is as follows：（1）Powder is prepared：According to equimolar than preparing each metal powder；（2）Powder mixes：Prepared powder is mixed in V-type and is uniformly mixed on powder machine；（3）Briquet：By mixed powder under forcing press cold-press moulding；（4）Molten alloy：Melting is carried out to the sample of briquet using vacuum non-consumable arc-melting furnace.It is BCC solid solution phases and a small amount of Laves phases that CrMoNbTiZr high-entropy alloys prepared by the present invention, which mainly form mutually, while having many advantages, such as that hardness height and corrosion resistance are strong.The alloy has good application prospect in wear-resisting and anti-corrosion field.
Description
Technical field
The present invention relates to a kind of high-entropy alloys and preparation method thereof, specifically, being related to a kind of wear-resisting, anti-corrosion
CrMoNbTiZr high-entropy alloys and preparation method thereof belong to alloy material and its preparing technical field.
Background technology
Traditional concept is the understanding of alloy property, alloy property can be improved by adding trace alloying element and
It improves, such as improves intensity, hardness, compression strength, corrosion resistance, thermal stability, but this method is not without disadvantage,
If addition can excessively lead to the even brittle complicated phase of a large amount of weld metal zone brittle intermetallic things occur so that the mechanicalness of alloy
It can reduce.In addition, compound can excessively have adverse effect on the research of alloy structure.Therefore, for a long time, scholar is opening
All it is using a kind of alloying element as pivot during sending out novel alloy and improving alloy（Generally more than 50%）, few using addition
It measures alloying element and improves the method for technique, to obtain the alloy of excellent tissue and performance.But with present industrial work
The high speed development of journey technology, the deficiency of homogenous material performance, which has become, restricts its difficulty further developed in engineering field
Topic.Therefore research staff, which increasingly tends to develop using new and high technology, prepares high performance new material, research and development intensity,
The all excellent new material of the properties such as toughness, hardness, it has also become the Main way of Material Field development.High-entropy alloy is as close
Occur a kind of simultaneously fast-developing novel high-strength alloy over year, receives the highest attention of Material Field expert.TaiWan, China
Luxuriant etc. the development framework for taking the lead in jumping out conventional alloys of the leaf of Tsinghua University, multicomponent high-entropy alloy has been put forward for the first time in 2004
Design philosophy, more pivot high-entropy alloys are generally with 5 kinds or 5 kinds or more of essential element, these essential elements are with equimolar
Than or approximate equimolar than configuration.The entropy of mixing of alloy is high, in process of setting, the analysis of brittlement phase in traditional multicomponent alloy
Go out suppressed, such as intermetallic compound；The single solid solution that BCC or FCC configuration are generally formed after solidification, greatly reduces more
The brittleness of first alloy.More pivot high-entropy alloys have been broken designs pattern by the conventional alloys of base of a kind of alloying element, can pass through
Alloying component optimization design, obtaining has the tissue such as microstructure simplification, nano-scaled precipitate, non crystalline structure, nanocrystal special
The excellent performance group of the high intensity, high rigidity, wear-resisting, corrosion-resistant, high temperature resistant creep, high temperature oxidation resisting, resistance to temper softening etc. of seeking peace
Alloy is closed, high pressure resistant, corrosion-resistant pressure vessels for the chemical industry and engineering high-strength corrosion-resistant part are widely used in.
Invention content
It is an object of the invention to develop wear-and corrosion-resistant high-entropy alloy --- the CrMoNbTiZr high with excellent properties
Entropy alloy makes it meet requirement of the people to material wear-resistant anti-corrosion performance in modern industry so that high-entropy alloy is led in application
It is used widely in domain.
The technical solution that the present invention takes to solve above-mentioned technical problem is：A kind of high entropy alloy material, ingredient are
CrMoNbTiZr, wherein Cr:Mo:Nb:Ti:The molar ratio of Zr is followed successively by：1:1:1:1:1.
The technical solution that the present invention takes to solve above-mentioned technical problem further includes：A kind of ingredient is CrMoNbTiZr's
The preparation method of high entropy alloy material, it is characterised in that be specifically realized by the following steps：
One, using metallurgical raw material Cr, Mo, Nb, Ti and Zr metal powder of 99.5% or more purity, according to equimolar ratio
It carries out accurate weigh to match, be mixed uniformly；
Two, it using pressure-like machine by mixed powder briquet, prepares alloy for melt and uses；
Three, using vacuum non-consumable electrode electric arc furnace molten alloy, block-like sample is placed on to the melting of periphery first
In slot, and pure titanium grain is placed in most intermediate melting slot, placement closes fire door after finishing, and tightens the closing of four, sample room
Knob；
Four, sample room is vacuumized, when vacuum degree reaches 5 × 10-3After Pa, be filled with purity be 99.99% argon gas until in stove
Pressure reaches half of atmospheric pressure, and repeats this step 2 ~ 3 time；The purpose that repetition vacuumizes is gas washing, and charge and discharge argon gas makes repeatedly
The air obtained in smelting furnace minimizes as possible；
Five, charge and discharge argon gas reaches half of atmospheric pressure until furnace pressure after vacuum exhausts, and can proceed by this time molten
Refining；It is as possible that remaining oxygen in stove is depleted first by the pure titanium grain melting one time in melting pond before melting sample；
Six, in order to make raw material be better mixed uniformly in fusion process, after each molten alloy fusing, the electric arc retention time
In 90 ~ 120s, is overturn, be so repeated 4 times above after alloy block cooling；
Seven, after melting is completed, according to the size shape of required product, the aluminium alloy after repetition melting can be cast in mould
It is then cooling to obtain in tool.
The principle of the present invention and advantageous effect are：
1. the present invention provides a kind of CrMoNbTiZr high-entropy alloys, the high-entropy alloy by simple structure solid solution phase
And a small amount of laves phase compositions, alloy structure is uniform, has higher hardness and excellent corrosion resistance, the alloy
Microhardness is up to 689HV.It has broad application prospects；
2. the present invention provides a kind of preparation methods of CrMoNbTiZr high-entropy alloys, using high vacuum alloy electric arc melting
It is prepared, preparation method is simple and reliable.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum of the CrMoNbTiZr high-entropy alloys prepared in embodiment.
Fig. 2 is the scanning electron microscopy tissue of the CrMoNbTiZr high-entropy alloys prepared in embodiment.
Specific implementation mode
Illustrate that the preparation method of the present invention and processing performance, those skilled in the art can by particular specific embodiment below
Advantages of the present invention and effect are comprehensively understood by content disclosed in the present specification.
1, CrMoNbTiZr high-entropy alloys composition design.
Present embodiment is a kind of CrMoNbTiZr high-entropy alloys being made of five kinds of elements of Cr, Mo, Nb, Ti and Zr,
In, Cr:Mo:Nb:Ti:The molar ratio of Zr is followed successively by：1:1:1:1:1.
2, the preparation of CrMoNbTiZr high-entropy alloys.
The preparation of high-entropy alloy is a step of most critical, and preparation process is as follows：
1）Raw material preparation：The alloy smelting raw material that the present invention uses is high-purity（Purity is 99.5% or more）Cr、Mo、Nb、Ti
With Zr elements, all dusty materials of raw material used；
2）It weighs and matches powder：Accurate weighing and proportioning is carried out according to molar ratio, and the dusty material mixing after weighing
Together, it is mixed using V-type and at the uniform velocity mixes 10h on powder machine；
3）Briquet：By the powder mixed with the pressure cold-press moulding of 200MPa on cold press, the dwell time is about
For 90-120s；
4）Melting high-entropy alloy：1. using vacuum non-consumable electrode electric arc furnace molten alloy, block-like sample is put first
It sets in peripheral four melting slots, and pure titanium grain is placed in most intermediate melting slot, placement closes fire door after finishing, and twists
Four, tight sample room closing knob；2. being vacuumized to sample room, when vacuum degree reaches 5 × 10-3After Pa, it is 99.99% to be filled with purity
Argon gas reaches half of atmospheric pressure until furnace pressure, and repeats this step 2 ~ 3 time；The purpose that repetition vacuumizes is gas washing, instead
Multiple charge and discharge argon gas makes the air in smelting furnace minimize as possible；3. charge and discharge argon gas is reached until furnace pressure after vacuum exhausts
To half of atmospheric pressure, melting can be proceeded by this time；First by the pure titanium grain melting one time in melting pond before melting sample,
It is as possible that remaining oxygen in stove is depleted；4. in order to make raw material be better mixed uniformly in fusion process, each melting is closed
After gold fusing, the electric arc retention time in 90 ~ 120s, is overturn after alloy block cooling, is so repeated 4 times above；5. melting
After completion, non-consumable vacuum arc melting furnace taking-up sample is opened after alloy cools to room temperature with the furnace, finally obtains one
The CrMoNbTiZr high-entropy alloy ingot castings of ellipsoid.
3, the institutional framework and performance of CrMoNbTiZr high-entropy alloys.
1）X-ray diffraction（XRD）Test and crystal species analysis
The ingot casting of acquisition is cut into the square sample of 5mm × 5mm × 4mm sizes using wire cutting, then successively by sample
It uses the abrasive paper for metallograph of 800#, 1200#, 1500# and 2000# carefully to grind successively, reuses polishing machine and be polished.X
X ray diffraction material phase analysis carries out on 2500 X-ray diffractometers of Rigaku Rigaku D/Max.Equipment and technology specification：Make
Use Cu as radiation source, graphite monochromator, operation voltage 40kV, electric current 250mA, rotation target.8 °/min of sweep speed, selection are spread out
Elevation range is 2 θ=5-90 °.Experimental data is analyzed using 6.0 softwares of MDI-Jade, determines object phase.As shown in Figure 1
The XRD test results of CrMoNbTiZr high-entropy alloys show that the main composition of CrMoNbTiZr high-entropy alloys is mutually body-centered cubic knot
Structure solid solution phase and a small amount of Laves phases.And Laves phases among these are mainly CrTi2、Mo3Nb intermetallic compounds.
2）Microscopic examination
The ingot casting of acquisition is cut into the square sample of 5mm × 5mm × 4mm sizes using wire cutting, then successively by sample
It uses the abrasive paper for metallograph of 800#, 1200#, 1500# and 2000# carefully to grind successively, reuses polishing machine and be polished.With
Scanning electron microscope observes sample tissue pattern.The cellular crystal tissue that CrMoNbTiZr high-entropy alloys generate as shown in Figure 2.
3）Microsclerometry and analysis
The ingot casting of acquisition is cut into the square sample of 5mm × 5mm × 4mm sizes using wire cutting, then successively by sample
It uses the abrasive paper for metallograph of 800#, 1200#, 1500# and 2000# carefully to grind successively, reuses polishing machine and be polished.It adopts
Test force with the hardness of HZr-1000 type microhardness testers test samples, the microhardness testers is 9.807N (1kgf), load
15s.Sample chooses 7 different locations and measures its microhardness, removes maximum hardness value and lowest hardness value, takes remaining hardness number
Microhardness value of the mean values as sample, the microhardness value for finally obtaining the alloy is 689HV.
4）The corrosion resistance of alloy
The ingot casting of acquisition is cut into the square sample of 5mm × 5mm × 4mm sizes using wire cutting, then successively by sample
It uses the abrasive paper for metallograph of 800#, 1200#, 1500# and 2000# carefully to grind successively, reuses polishing machine and be polished.It will
The good sample of grinding and polishing is put into alcohol cleans 30min, and dry weighing with ultrasonic washing instrument, later distinguishes sample complete
Immerse a concentration of 5%, 15%, 30% HNO3Solution and 3.5% NaCl solution in, keep 6h, 12h, for 24 hours, take after 48h, 96h
Go out, the front and back specimen surface state of analysis corrosion and weight change.
As seen from Table 1, mass change very little of the alloy in different corrosive liquids, and there are few change, tables on the surface of alloy
CrMoNbTiZr high-entropy alloys prepared by bright the application have excellent corrosion resistance.
In 1 example of table CrMoNbTiZr high-entropy alloys 3.5% NaCl solution and 5%, 15%, 30% HNO3 solution in
Impregnate the mass change after 96h
| Etchant solution | 3.5%NaCl | 5%HNO3 | 15%HNO3 | 30%HNO3 |
| Quality/g before corrosion | 0.7359 | 0.6776 | 0.7663 | 0.7219 |
| Quality/g after corrosion | 0.7360 | 0.6786 | 0.7668 | 0.7210 |
| Mass change/g | 0.0001 | 0.0010 | 0.0005 | -0.0009 |
Claims (2)
1. a kind of high entropy alloy material, it is characterised in that：The high-entropy alloy ingredient is CrMoNbTiZr, wherein Cr:Mo:Nb:
Ti:The molar ratio of Zr is followed successively by：1:1:1:1:1；The preparation method of the CrMoNbTiZr high entropy alloy materials, it is characterised in that
It is specifically realized by the following steps：
One, it using Cr, Mo, Nb, Ti and Zr metal powder, carries out accurate weigh according to equimolar ratio and matches, be mixed
Uniformly；
Two, it using pressure-like machine by mixed powder briquet, prepares alloy for melt and uses；
Three, using vacuum non-consumable electrode electric arc furnace molten alloy, block-like sample is placed in the melting slot of periphery first,
And be placed on pure titanium grain in most intermediate melting slot, placement closes fire door after finishing, and tightens four, sample room closing knob；
Four, sample room is vacuumized, when vacuum degree reaches 5 × 10-3After Pa, be filled with purity be 99.99% argon gas until stove internal pressure
Power reaches half of atmospheric pressure, and repeats this step 2~3 time；The purpose that repetition vacuumizes is gas washing, and charge and discharge argon gas makes repeatedly
Air in smelting furnace minimizes as possible；
Five, charge and discharge argon gas reaches half of atmospheric pressure until furnace pressure after vacuum exhausts, and can proceed by melting at this time；
It is as possible that remaining oxygen in stove is depleted first by the pure titanium grain melting one time in melting pond before melting sample；
Six, in order to make raw material be better mixed uniformly in fusion process, after each molten alloy fusing, the electric arc retention time is 90
~120s is overturn after alloy block cooling, is so repeated 4 times above；
Seven, after melting is completed, according to the size shape of required product, the aluminium alloy after repetition melting can be cast in mold
It is interior, it is then cooling to obtain.
2. high entropy alloy material according to claim 1, it is characterised in that Cr, Mo, Nb, Ti and Zr described in step 1
The purity of metal powder is 99.5% or more.
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| CN108220740B (en) * | 2018-01-15 | 2020-07-07 | 湘潭大学 | Wear-resistant and corrosion-resistant high-entropy alloy material and preparation method thereof |
| CN108441744B (en) * | 2018-02-06 | 2020-04-21 | 湘潭大学 | Self-lubricating antifriction wear-resistant alloy material and preparation method thereof |
| CN108220741B (en) * | 2018-02-14 | 2019-11-05 | 哈尔滨工业大学 | A kind of bio-medical high-entropy alloy and preparation method thereof |
| CN109161776A (en) * | 2018-10-10 | 2019-01-08 | 湘潭大学 | A kind of porous high-entropy alloy of pre-alloyed CrMoNbTiZr and preparation method thereof |
| CN109252199A (en) * | 2018-11-23 | 2019-01-22 | 西安工业大学 | A kind of high entropy alloy material of surface ceramic deposition and preparation method thereof |
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| CN110358964B (en) * | 2019-07-24 | 2021-11-05 | 中国科学院金属研究所 | MoVNbTiCr for nuclear powerxHigh-entropy alloy and preparation method thereof |
| CN111058076B (en) * | 2019-12-30 | 2020-11-20 | 安徽工业大学 | Zr-based high-entropy alloy material and method for synthesizing porous spherical structure on surface of Zr-based high-entropy alloy |
| CN111850372B (en) * | 2020-06-23 | 2021-12-07 | 湘潭大学 | A series of FeCoCrNiW (VC)XPreparation of high-entropy alloy and precipitation strengthening process thereof |
| CN112553517B (en) * | 2020-12-04 | 2022-06-21 | 湘潭大学 | Preparation method and process of wear-resistant CrMoNiTaHfW high-entropy alloy |
| CN115505813B (en) * | 2022-09-20 | 2023-05-23 | 中国科学院兰州化学物理研究所 | B-doped high-entropy alloy wear-resistant material with multistage precipitation strengthening function, and preparation method and application thereof |
| CN116024480B (en) * | 2023-01-10 | 2024-10-11 | 昆明理工大学 | High-entropy alloy material and preparation method thereof |
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| KR101728936B1 (en) * | 2014-07-28 | 2017-04-21 | 세종대학교산학협력단 | High entropy alloy having excellent strength and ductility |
| CN105671392B (en) * | 2014-11-19 | 2017-11-03 | 北京科技大学 | A kind of TiZrHfNb base high-entropy alloys of nitrogen reinforcing and preparation method thereof |
| CN105671404B (en) * | 2014-11-19 | 2017-11-03 | 北京科技大学 | A kind of TiZrHfNb base high-entropy alloys of the common alloying of nitrogen oxygen and preparation method thereof |
| KR101708763B1 (en) * | 2015-05-04 | 2017-03-08 | 한국과학기술연구원 | Bcc alloys with strong resistance against high temperature neutron irradiation damage |
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