CN110373595A - A kind of high entropy high temperature alloy of high-performance and preparation method thereof - Google Patents

Abstract

The present invention relates to metallurgical technology fields, and in particular to a kind of high entropy high temperature alloy and preparation method thereof.The present invention is directed to current high temperature alloy preparation process challenge, and the high entropy of mixing of high-entropy alloy, big distortion of lattice and sluggish diffusion effect is utilized, and provides a kind of high entropy high temperature alloy and preparation method thereof.Provided technical solution is: a kind of high entropy high temperature alloy, and ingredient expression formula is (Al_aCo_bFe_cNi_dC_f)_100‑g‑M_G,Preparation method is to obtain the high entropy high temperature alloy of nanometer coherence strengthening FCC base by directly solidifying.Product of the invention shows the feature similar with conventional high-temperature alloy high-temp performance, has excellent mechanical behavior under high temperature.

Description

A kind of high entropy high temperature alloy of high-performance and preparation method thereof

Technical field

The present invention relates to metallurgical technology fields, and in particular to a kind of high entropy high temperature alloy alloy and preparation method thereof.

Background technique

High-entropy alloy is a kind of novel alloy developed in recent years, has high entropy effect thermodynamically, the crystalline substance in structure " cocktail " effect in lattice distortion effect, kinetically sluggish diffusion effect and performance.Therefore, high-entropy alloy, especially Nanometer coherence strengthening FCC matrix high-entropy alloy, has the potentiality applied as high-temperature structural material.

Currently, the report about coherence second-phase strength FCC base high-entropy alloy is relatively more, high-entropy alloy is discussed mostly Room temperature and cryogenic property, as C. T. Liu reports (FeCoNi)_100-x-yAl_xTi_ySerial L1₂Mutually strengthen FCC base high-entropy alloy, But L2 is precipitated₁Phase does not report its high-temperature behavior；Y. Tong research discovery FeCoNiCrTi_0.2High-entropy alloy has L1₂Mutually altogether Lattice nanometer phase has excellent room temperature and cryogenic mechanics performance；Xue Yunfei is in 105755324 A, CN 108193088 of patent CN A etc. reports Al-Cr-Fe-Ni-V system high-entropy alloy, and there are a large amount of coherence L1₂Phase, comprehensive mechanical property is excellent, but there are crisp The Laves phase of property, still only has studied its room-temperature mechanical property.In addition, patent CN 105112759 A and CN 107747019 The high temperature alloy of the reports such as A is the infusibility high-entropy alloy of dystectic refractory alloy element preparation, rather than coherence nanometer mutually increases Strong FCC base high-entropy alloy；104694808 A of patent CN reports L1₂Coherence nanometer mutually enhances the high temperature of FCC base high-entropy alloy Stretching and high-temerature creep, but inevitably occur L2 in alloy₁Brittle phase, at the same also need complicated cold working with And heat treatment process.

Summary of the invention

The present invention is directed to current high temperature alloy preparation process challenge, and the high entropy of mixing of high-entropy alloy, big lattice is utilized Distortion and sluggish diffusion effect provide a kind of high entropy high temperature alloy alloy and preparation method thereof.

To achieve the above object, the technical solution adopted by the present invention are as follows:

A kind of high entropy high temperature alloy of high-performance mutually enhances the high entropy high temperature alloy of FCC base, institute by directly solidifying acquisition nanometer coherence The high entropy high temperature alloy composition expression formula stated is Al_aCo_bFe_cNi_dC_e, by+e=1 group atomic percentage a+b+c+d At, and 0.03≤a≤0.27,0.2≤b≤0.6,0 < c≤0.3,0.1≤d≤0.6,0.01≤e≤0.06.

Further, the high entropy high temperature alloy composition expression formula is (Al_aCo_bFe_cNi_dC_e)_100-f-M_f, M is alloying Element, M are one or more of Cr, Cu, Hf, Nb, Mn, Mo, Ta, Ti, V, W, Zr and rare earth element, and wherein additive amount is not More than the 5% of alloy atom amount summation.

Further, the raw material impurity content is lower than 0.1%.

The preparation method of high-performance high temperature high-entropy alloy, comprising the following steps:

1) ingredient: above-mentioned technical pure metallic element is mechanically first removed, ingredient, C element are difficult to dissolve in metal, adopt according to the ratio Use phosphorus-containing alloy；

2) vacuumize: melting furnace chamber is evacuated to 3.0 × 10^-3Pa is passed through in the high-purity argon gas to furnace that purity is 99.99wt.% Gauge pressure is -0.05MPa；

3) melting: melting is carried out using arc-melting furnace, 3 titanium sponge deoxygenations of melting, each duration 2min, alloy pig turns over Peritectic, which refines 5 times, makes ingredient uniform, and opens electromagnetic agitation and be sufficiently stirred, and each smelting time continues 2 min, and melting is complete Cheng Hou is cooled to room temperature sampling, obtains high temperature high-entropy alloy ingot casting.

Advantages of the present invention:

1, high entropy high temperature alloy provided by the invention has excellent compressive property, is more than tradition in most of temperature range The mechanical property of Ni base, Co base, B2/BCC high-entropy alloy and part infusibility high-entropy alloy；

2, the high entropy high temperature alloy of face-centered cubic prepared by the present invention, with nano-scale rank coherence reinforced phase, and have compared with Form, the volume for changing the method adjusting nanometer phase of solidification cooling rate and alloying can also be used in big constituent adjustment space Score and size, thus adjust the comprehensive performance of alloy；

3, the present invention, which can prepare nanometer coherence mutually using the method directly solidified, enhances the high entropy high temperature alloy of FCC base, does not need Complicated cold working and heat treatment process, technical process is simple, has the advantages of economic, low energy consumption, low-carbon environment-friendly.

Detailed description of the invention

Fig. 1 as cast condition (Al_aCo_bFe_cNi_dC_e)_100-f-M_fHigh entropy high temperature alloy XRD spectrum；

Fig. 2 is as cast condition (Al_aCo_bFe_cNi_dC_e)_100-f-M_fHigh entropy high temperature alloy SEM photograph, (a) are Al_0.3CoFeNiC_0.1 SEM Photo；It (b) is Al_0.5CofeNiC_0.1SEM photograph；It (c) is (Al_0.3CoFeNiC_0.1)₉₉Cu SEM photograph (d) is (Al_0.5CoFeNiC_0.1)_99.8Ta_0.2SEM photograph；

Fig. 3 Al_0.5CoFeNiC_0.1Nanometer phase constitution under different cooling rate, (a) are high entropy high temperature alloy after casting Al_0.5CoFeNiC_0.1TEM result；(b) high entropy high temperature alloy Al after copper roller is quickly cooled down_0.5CoFeNiC_0.1TEM result；

Fig. 4 as cast condition (Al_aCo_bFe_cNi_dC_e)_100-f-M_fHigh entropy high temperature alloy TEM is as a result, (a) is Al_0.3CoFeNiC_0.1TEM knot Fruit；It (b) is Al_0.5CoFeNiC_0.1TEM result；

Fig. 5 Al_0.3CoFeNiC_0.1Compression curve under different temperatures；

Fig. 6 Al_0.5CoFeNiC_0.1Compression curve under different temperatures；

Fig. 7 Al_0.5CoFeNiC_0.1It is compared with the yield strength of other alloys.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.

Raw material used in the embodiment of the present invention is all made of Al, Co, Fe, Ni, the Fe-C of purity not less than 99.9wt.% and closes Gold and element M, element M are one or more of Cr, Cu, Hf, Nb, Mn, Mo, Ta, Ti, V, W, Zr and rare earth element, Mechanically remove surface oxide skin, and use industry anhydrous ethanol ultrasonic cleaning metal, according to experiment use purity not Pure metal or alloy lower than 99.9wt.%.

Embodiment 1:(Al_aCo_bFe_cNi_dC_e)_100-f-M_fThe preparation and XRD result of high entropy high temperature alloy

Step 1: ingredient.

Ingredient is carried out by the ingredient formula of table 1, respectively weighs 130g mixture, wherein element M is the alloying member for addition Element.

(Al in 1 example 1 of table_aCo_bFe_cNi_dC_e)_100-f-M_fHigh entropy high temperature alloy composition proportion

Step 2: vacuumizing.Load weighted material is placed in the water jacketed copper crucible cleaned out in advance, electric arc furnaces vacuum is evacuated to 3.0×10^-3Pa is filled with the high-purity argon gas that protection gas purity is 99.99wt.%, makes gauge pressure -0.05Pa in furnace.

Step 3: melting.Melting is carried out using vacuum copper crucible water cooling arc-melting furnace.In order to which the oxygen reduced in furnace contains Amount absorbs remnant oxygen in furnace by the pure titanium of molten state first by pure titanium melting 3 times.When melting, opens electromagnetic agitation and carry out It is sufficiently stirred, each smelting time continues 2 min, the swing arc rifle in melting.In order to keep alloying component uniform, in melting Cheng Zhong, and it is each all over having melted, overturning spoon overturning alloy pig to be cooled is at least overturn melting 5 times.After the completion of melting, it is cooled to Room temperature prepares uniform high entropy high temperature alloy ingot casting.Then can also remelting be cast into plate, bar, using high speed rotation Copper roller obtain the band etc. being quickly cooled down.

Referring to Fig. 1, Al is shown in map_0.3CoFeNiC_0.1、(Al_0.3CoFeNiC_0.1)_99.9 Cu_0.1、 Al_0.5CoFeNiC_0.1、Al_0.5CoFeNiC_0.2(Al_0.5CoFeNiC_0.1)_99.5Ta_0.5The XRD spectrum of five kinds of cast alloy.It can be with It was found that there is nano-scale hardening constituent in shown high entropy high temperature alloy.Fig. 2 (a) is that XRD diffraction spectra three strongest peak corresponds to FCC Phase, and all shown the superstructure diffraction maximum of (100) family of crystal planes.The result shows that this kind of alloy is mainly based on FCC phase, and deposit In the second phase of coherence, this is similar with conventional alloys coherence the second phase diffraction maximum.TEM also susceptible of proof hereinafter.

Embodiment 2:(Al_aCo_bFe_cNi_dC_f)_100-g-M_gThe preparation and tissue SEM pattern result of high entropy high temperature alloy

Carry out ingredient respectively by table 2, successively according to embodiment 1 vacuumize and melting step, obtain as cast condition of the present invention High entropy high temperature alloy.

(Al in 2 example 2 of table_aCo_bFe_cNi_dC_e)_100-f-M_fHigh entropy high temperature alloy composition proportion

Fig. 2 is (Al_aCo_bFe_cNi_dC_e)_100-f-M_fSem analysis result.Cast alloy SEM result has Al_0.3CoFeNiC_0.1、 Al_0.5CoFeNiC_0.1、(Al_0.3CoFeNiC_0.1)₉₉Cu and (Al_0.5CoFeNiC_0.1)_99.8Ta_0.2.As can be seen that shown in Fig. 2 (a) Al_0.3CoFeNiC_0.1The nanometer phase average of high entropy high temperature alloy is having a size of 16nm, volume fraction 27%；Al_0.5CoFeNiC_0.1It is high Entropy high temperature alloy nano particle average-size is 35nm, and volume fraction is 48.5% (Fig. 2 (b))；(Al_0.3CoFeNiC_0.1)₉₉Cu High entropy high temperature alloy nano particle reduces 5nm or so, and particle mean size is only 11nm, and volume fraction increases, and reaches 32%, such as Fig. 2 (c)；(Al_0.5CoFeNiC_0.1)_99.8Ta_0.2High entropy high temperature alloy compares Al_0.5CoFeNiC_0.1Alloy average-size is almost Reduce half, only 13nm, volume fraction reaches 53%, such as Fig. 2 (d).Addition Cu and Ta alloy element refined nanometer phase and Increase nanometer phase volume fraction.This shows the size, volume fraction and form that can regulate and control nanometer phase by alloy element.From TEM photo can also further illustrate.

Embodiment 3:(Al_aCo_bFe_cNi_dC_e)_100-f-M_fTEM tissue after the high entropy high temperature alloy difference type of cooling

Step 1: ingredient.By a=13.88%, b=c=d=27.78%, f=2.78%, g=0 and a=13.88%, b=c When=d=27.78%, when e=2.78%, f=0,140g mixture is weighed, carries out ingredient, the step of according to embodiment 1, according to It is secondary vacuumize, melting, obtain high entropy high temperature alloy ingot, then intercept the induction heating remelting in quartz ampoule of 10g sample, utilize copper roller Outer surface (10m/s) is quickly cooled down, and is obtained and is quickly cooled down high entropy high temperature alloy band.Remainder be cast to internal diameter 12mm × In the copper mold of 70mm, high entropy high temperature alloy casting bar is obtained.High entropy high temperature after thus obtaining different cooling speed solidification closes Gold.

Fig. 3 show Al under different cooling_0.5CoFeNiC_0.1The nanometer phase TEM photo of high entropy high temperature alloy.Casting Bar cooling rate in copper mold is smaller, is cast into the bar of 12mm × 70mm, and copper roller is quickly cooled down cold cooling rate It is larger, form the band of 90 μ m-thicks.It can see that from figure, the average-size of nanometer phase is 35nm in the high entropy high temperature alloy of bar Square block, volume fraction is up to 48%, and such as Fig. 3 (a), and the average-size of band nanometer phase after rate is higher is 23nm's Spherical shape, volume fraction 38%, such as Fig. 3 (b).It follows that a nanometer ruler for coherence phase can be regulated and controled by changing cooling rate Very little, form and volume fraction.

Embodiment 4:(Al_aCo_bFe_cNi_dC_e)_100-f-M_fThe preparation of high entropy high temperature alloy and nanometer phase crystal structure

By a=b=c=d=23.81%, e=4.76%, f=0 and a=13.88%, when b=c=d=27.78%, e =2.78%, f=0 carries out ingredient respectively, the step of according to embodiment 1, successively by vacuumizing and melting, obtains AlCoFeNiC_0.2And Al_0.5CoFeNiC_0.1Two kinds of high entropy high temperature alloys of as cast condition of the present invention.Fig. 4 is (Al_aCo_bFe_cNi_dC_e)_100-g-M_gTem analysis result.Two kinds of alloy TEM are shown in figure as a result, by a, b, c, d and e letter It is melted into simple atomic ratio, i.e. cast alloy has AlCoFeNiC_0.2And Al_0.5CoFeNiC_0.1.From TEM result it is found that nanometer phase At a cube square block, by corresponding diffraction pattern it is found that the nanometer phase of two kinds of alloys and matrix are symbiosis and epibiosis, as orderly FCC nanometers mutually enhance the high entropy high temperature alloy of FCC base.This is consistent with XRD spectrum result shown in Fig. 1.

Embodiment 5:(Al_aCo_bFe_cNi_dC_e)_100-f-M_fThe preparation of high entropy high temperature alloy and Compressive Mechanical Properties

By a=8.82%, b=c=d=29.41%, e=2.95%, f=0 and a=13.88%, b=c=d=27.78% When, e=2.78%, f=0 carries out ingredient respectively, the step of according to embodiment 1, finally obtains the high entropy of as cast condition of the present invention High temperature alloy.Fig. 5 and Fig. 6 is respectively high entropy high temperature alloy Al_0.3CoFeNiC_0.1And Al_0.5CoFeNiC_0.1Compression curve.It can With discovery, Al_0.3CoFeNiC_0.1High entropy high temperature alloy is increased with compression temperature, yield strength abnormal phenomena occurs, Al_0.5CoFeNiC_0.1High entropy high temperature alloy is increased with temperature, and yield strength decrease speed is more slow.These phenomenons and tradition The surrender abnormal phenomenon of high temperature alloy is consistent, this high entropy high temperature alloy for showing that the present invention is designed and preparing has conventional high-temperature The characteristics of alloy.

Embodiment 6:(Al_aCo_bFe_cNi_dC_f)_100-g-M_gThe preparation of high entropy high temperature alloy and Compressive Mechanical Properties and other conjunctions The comparison of gold

By a=13.88%, when b=c=d=27.78%, e=2.78%, f=0 carries out ingredient respectively, according to embodiment 1 Step obtains Al_0.5CoFeNiC_0.1The high entropy high temperature alloy of as cast condition.Al shown in Fig. 7_0.5CoFeNiC_0.1High entropy high temperature alloy is in room When temperature is to 700 DEG C, yield strength is higher than many Ni bases, Co based high-temperature alloy and Fe base high-entropy alloy and infusibility high-entropy alloy. When temperature is higher than 700 DEG C, yield strength can compare favourably with 718 high temperature alloy of Inconel, show excellent high temperature Compression performance.Present invention point more outstanding is that the designed high-entropy alloy with preparation of the present invention does not need at complicated heat Reason and the cold-working process, directly solidification can obtain the high entropy high temperature alloy of nano-scale coherence strengthening FCC base.

The above, section Example only of the invention, is not intended to limit the scope of the present invention.

Claims (4)

1. a kind of high entropy high temperature alloy of high-performance, it is characterised in that: mutually enhance FCC base height by directly solidifying acquisition nanometer coherence Entropy high temperature alloy, the high entropy high temperature alloy composition expression formula are Al_aCo_bFe_cNi_dC_e, by atomic percentage a+b+c + d+e=1 is formed, and 0.03≤a≤0.27,0.2≤b≤0.6, and 0 < c≤0.3,0.1≤d≤0.6,0.01≤e≤ 0.06。

2. the high entropy high temperature alloy of high-performance according to claims 1 and 2, it is characterised in that: the high entropy high temperature alloy Ingredient expression formula is (Al_aCo_bFe_cNi_dC_e)_100-f-M_f, M is alloy element, M be Cr, Cu, Hf, Nb, Mn, Mo, Ta, Ti, V, W, one or more of Zr and rare earth element, wherein additive amount is no more than the 5% of alloy atom amount summation.

3. the high entropy high temperature alloy of high-performance according to claim 2, it is characterised in that: the raw material impurity content is lower than 0.1%。

4. the preparation method of high-performance high temperature high-entropy alloy according to claim 1, it is characterised in that: including following step It is rapid:

1) ingredient: above-mentioned technical pure metallic element is mechanically first removed, ingredient, C element are difficult to dissolve in metal, adopt according to the ratio Use phosphorus-containing alloy；

2) vacuumize: melting furnace chamber is evacuated to 3.0 × 10^-3Pa is passed through table in the high-purity argon gas to furnace that purity is 99.99wt.% Pressure is -0.05MPa；

3) melting: melting is carried out using arc-melting furnace, 3 titanium sponge deoxygenations of melting, each duration 2min, alloy pig turns over Peritectic, which refines 5 times, makes ingredient uniform, and opens electromagnetic agitation and be sufficiently stirred, and each smelting time continues 2 min, and melting is complete Cheng Hou is cooled to room temperature sampling, obtains high temperature high-entropy alloy ingot casting.