CN109022987A - A kind of width warm area negative expansion Laves phase alloy and preparation method thereof - Google Patents

A kind of width warm area negative expansion Laves phase alloy and preparation method thereof Download PDF

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CN109022987A
CN109022987A CN201810920668.6A CN201810920668A CN109022987A CN 109022987 A CN109022987 A CN 109022987A CN 201810920668 A CN201810920668 A CN 201810920668A CN 109022987 A CN109022987 A CN 109022987A
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warm area
laves phase
phase alloy
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CN109022987B (en
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王萌
黎隆富
林建超
童鹏
孙玉平
宋文海
朱雪斌
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Hefei Institutes of Physical Science of CAS
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    • C—CHEMISTRY; METALLURGY
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Abstract

The invention proposes a kind of wide warm area negative expansion Laves phase alloy, general formula Hf1‑x‑yZryTaxFe2, wherein 0.1≤x≤0.13,0≤y≤0.2.By controlling Ta component, the negative expansion warm area of the material is broadened, and move it to room temperature, while there is excellent mechanicalness and thermal conductivity, electrical conductance, be with a wide range of applications；Simultaneously because Zr is the major impurity in Hf raw material, cost of material can be substantially reduced using the Hf of low-purity as raw material.The present invention also provides a kind of preparation methods of wide warm area negative expansion Laves phase alloy.

Description

A kind of width warm area negative expansion Laves phase alloy and preparation method thereof
Technical field
The present invention relates to negative expansion Laves phase alloy field of material technology more particularly to a kind of wide warm area negative expansions Laves phase alloy and preparation method thereof.
Background technique
The volume of most of materials increases as temperature increases in nature, becomes smaller as temperature reduces, shows The characteristic expanded with heat and contract with cold.This intrinsic attribute brings inconvenience and harm to the practical application of material.For example, expanding with heat and contract with cold The stability that caused heat fatigue or mechanical fatigue will lead to device reduces, even with the lost of life；The optics of some precisions Instrument can cause error because of core component expanded by heating.Further, since in device each material expansion coefficient mismatch, temperature It will lead to dimensional mismatch when variation, equipment performance substantially reduces.With human society progress and science and technology rapid development, It is also increasingly harsher to the thermal stability requirement of material and device size.Such as in micro-nano device, aerospace, information communication etc. In field, it is often necessary to which material has extremely low temperature sensitivity and very high dimensional stability, i.e., regardless of environment temperature Variation, volume can be held essentially constant.Therefore, the material with negative expansion characteristic (can be compound with positive expanding material Prepare low-expansibility compound material) or functional material with low expansion character attract more and more extensive research interest.It is negative Thermal expansion material refer to material have with the antipodal hot expansion property of conventional material, i.e., in a certain warm area, with temperature It increases, the volume of material becomes smaller instead.Traditional negative expansion material mainly includes ZrW2O8Family, cubic phase trifluoride, PbTiO3Based compound, (Bi, La) NiO3Based compound, stratiform ruthenate, the manganese-based nitride of anti-perovskite structure, La (Fe, Co,Si)13And MnCoGe related compound etc..
In general, by metallicity negative expansion (the Negative Thermal with high conductance, thermal conductivity Expansion, NTE) material and metal just expand (Positive Thermal Expansion, PTE) Material cladding can be more The excellent properties of good reservation fertile material.Thus relative to ceramic negative expansion material, metallicity negative expansion material has more advantage. In addition, local temperature rising, therefore chip will be rapidly resulted in when that can not radiate in time in the chip operation in microelectronic component (such as cooling fin, welding position) generates thermal stress due to expansion coefficient mismatch between connected components, this will seriously affect electronics The reliability and service life of device.As the blender of the coefficient of expansion, metal class NTE material conducts heat is rapid and uniform.However Although the NTE material of the continuous exploratory development of scientific research personnel, this kind of metallicity is still very rare.
The Laves phase compound Hf of hexagonal structure1-xTaxFe2(0.16 x≤0.22 <) shows precipitous when the temperature rises Ferromagnetic-paramagnetic phase transformation.Along with phase transformation, volume shrinkage mass Δ V/V is up to 1%, but due to the essence of its first order phase change, The temperature window of this Lattice Contraction is very narrow (several Kelvins), can not obtain practical application.
Summary of the invention
The invention proposes a kind of wide warm area Laves phase metal negative expansion material, general formula Hf1-x-yZryTaxFe2, wherein 0.1≤x≤0.13,0≤y≤0.2 have broadened the negative expansion warm area of the material, have reached phase transition temperature by controlling Ta component To room temperature, while there is excellent mechanicalness and thermal conductivity, electrical conductance, is with a wide range of applications；Simultaneously because Zr is Hf original Major impurity in material can substantially reduce cost of material using the Hf of low-purity as raw material, and the present invention also provides a kind of width The preparation method of warm area negative expansion Laves phase alloy.
A kind of wide warm area negative expansion Laves phase alloy that the present invention also proposes, general formula Hf1-x-yZryTaxFe2, wherein 0.1≤x≤0.13,0≤y≤0.2.
Preferably, the wide warm area negative expansion Laves phase alloy is in T1~T2Negative expansion property is shown in warm area, 222K≤T1≤ 287K, 327K≤T2≤ 356K, the temperature difference T of negative expansion warm area are 69K~112K.
Preferably, the average linear coefficient of expansion α of the wide warm area negative expansion Laves phase alloyLFor -10.7~- 16.3ppm/K。
Preferably, work as x=0.13, when y=0, gained width warm area negative expansion Laves phase alloy obtains the negative heat of wide warm area Expand Laves phase alloy Hf0.87Ta0.13Fe2In the average linear coefficient of expansion α of warm area 277K~327KLFor -29.3ppm/K.
Preferably, in a particular embodiment, the Zr in the wide warm area negative expansion Laves phase alloy derives from raw material Hf Impurities Zr in metal.
In practical applications, it would be desirable to consider the price of raw material.Simple Hf is very rare in nature, but It is present in zirconium ore object and (at least accounts for 5%).Again since Hf and Zr are closely similar in the chemically, it is difficult to separate, therefore high-purity Hf price it is generally also very high, and the impurity in Hf metal is mainly Zr.Therefore, studying Zr impurity contained in Hf metal is It is no to will affect Hf1-xTaxFe2NTE performance in material is also very necessary.Then we are prepared for Hf1-x-yZryTaxFe2Change It closes object and measures its hot expansion property.
Work as x=0.1 as can be seen from Figure 3, when y is respectively 0,1,2, Hf1-x-yZryTaxFe2The average linear of material expands Factor alphaLAs the increase of Zr doping y is slowly increased, while NTE warm area is broadened to low temperature significantly.When (Hf's is pure by y=0.2 77.8%) degree is equivalent to, Δ T is up to 112K (240K-352K).And when the purity of Hf drops to 99.5% from 99.9%, it An order of magnitude has also dropped in price.Above-mentioned the results show selection purity lower Hf metal prepares NTE material Hf1-x- yZryTaxFe2Material negative thermal expansion performance is had no effect on, low temperature warm area has been broadened instead, and significantly reduce cost, has more passed through It helps practical.
The present invention also provides a kind of wide warm area negative expansion Laves phase alloy preparation method, include the following steps: by According to Fe, Hf, Ta, Zr in Hf1-x-yZryTaxFe2In stoichiometric ratio weigh raw material, be placed under argon atmosphere that carry out electric arc molten Refining, then anneals under vacuum conditions, and annealing temperature is 900-1100 DEG C, obtains the width warm area negative expansion Laves and is harmonious Gold.
Preferably, annealing temperature is 1000 DEG C, and annealing time is 7 days.
Preferably, electric arc melting more than six times, stirs ingot casting once after the completion of each electric arc melting, it is ensured that ingot casting ingredient Uniformity.
Preferably, the concrete operations annealed under vacuum condition are as follows: the ingot casting after electric arc melting is placed in quartz ampoule, so Quartz ampoule is evacuated to vacuum afterwards and is sealed, sealed silica envelope is placed in chamber type electric resistance furnace and is annealed.
The present invention by adjusting hexagonal structure Laves phase compound Hf1-xTaxFe2Middle Ta doping content (0.1≤x≤ 0.13) Hf, has been broadened significantly1-xTaxFe2The negative expansion warm area of material makes phase transition temperature reach room temperature, such as containing as Ta When amount is x=0.13, Hf0.87Ta0.13Fe2Material negative thermal expansion warm area Δ T reaches 105K (222K-327K), covers room temperature, Average linear negative thermal expansion coefficient αLFor -16.3ppm/K.Wherein (277K-327K, Δ T=in almost linear negative expansion warm area 50K), αL=-29.3ppm/K.This negative thermal expansion coefficient is commercial negative expansion material ZrW2O8Three times of (- 9ppm/K), while The coefficient of expansion (such as the Al, α of most metals are surmountedL=23ppm/K).Gained Hf simultaneously1-xTaxFe2Material is at room temperature Thermal conductivity up to 10.5W (mK)-1, have also exceeded other alloy negative expansion material (LaFe at room temperature10.5Co1.0Si1.5's K value is 6W (mK)-1, Cu0.6Si0.05Ge0.35NMn3For 3.7W (mK)-1, Mn0.98CoGe is 7W (mK)-1).It is excellent The thermal stress that good heating conduction can be subject in thermal cycle with lightening material also avoids the microdevice of connection due to local hair Performance degradation caused by heat has very big advantage in practical applications.Hf1-xTaxFe2Material Vickers hardness is more than 850Hv, poplar Family name's modulus is more than 200GPa, has good mechanical performance, conducive to the performance for enhancing positive swollen matrix material.And biggish volume Modulus means that less additional amount can offset the positive expansion of basis material, has to simple, light weight composite material is designed It is significant.
In addition, the present invention has studied Zr impurity contained in Hf metal to Hf1-xTaxFe2Negative expansion performance in material It influences, is prepared for Hf1-x-yZryTaxFe2Material simultaneously measures its hot expansion property.For example, for Hf0.9-yZryTa0.1Fe2Chemical combination Object, with the increase of Zr doping y, negative expansion warm area is broadened to low temperature significantly, and the absolute value of negative thermal expansion coefficient slightly has It improves.When y=0.2 (purity of Hf is equivalent to 77.8%), negative expansion warm area Δ T reaches 112K (240K-352K), and average line is swollen Swollen factor alphaLFor -12.43ppm/K.As it can be seen that if using low pure Hf raw metal, prepared Hf1-xTaxFe2Material still has Standby excellent negative expansion property.And the reduction due to requiring raw material Hf metal purity, the cost of production is greatly reduced, It is more economical practical.
Detailed description of the invention
Fig. 1 (a) be the embodiment of the present invention 1, embodiment 3, the wide warm area negative expansion Laves phase alloy of the gained of embodiment 4 and Reference examples 1, reference examples 2, reference examples 3, reference examples 4, the linear heat of 5 gained Laves phase metal negative thermal expansion material of reference examples are swollen Swollen (Δ L/L) varies with temperature curve；Fig. 1 (b) is the embodiment of the present invention 1, the wide negative heat of warm area obtained by embodiment 3, embodiment 4 is swollen The average linear of swollen Laves phase alloy thermally expands (αL) size and corresponding warm area.
Fig. 2 be the wide warm area negative expansion Laves phase alloy lattice parameter of the gained of the embodiment of the present invention 3 (Volume and Lattice constant) vary with temperature curve.
Fig. 3 is the linear thermal expansion of embodiment 1, embodiment 5, the wide warm area negative expansion Laves phase alloy of 6 gained of embodiment (Δ L/L) varies with temperature curve and average linear thermal expansion (αL) size and corresponding warm area.
Fig. 4 (a) is 4 gained of embodiment 1, the wide warm area negative expansion Laves phase alloy of 4 gained of embodiment and reference examples The thermal conductivity (k) of Laves phase metal negative thermal expansion material varies with temperature curve；Fig. 4 (b) is embodiment 1,4 gained of embodiment The conductivity (σ) of 4 gained Laves phase metal negative thermal expansion material of wide warm area negative expansion Laves phase alloy and reference examples with Temperature variation curve.
Fig. 5 (a) is embodiment 1, embodiment 3, the wide warm area negative expansion Laves phase alloy of 4 gained of embodiment and reference examples 1,2 gained Laves phase metal negative thermal expansion material of reference examples hardness (H at room temperaturev)；Fig. 5 (b) is embodiment 1, implements Example 3, the wide warm area negative expansion Laves phase alloy of 4 gained of embodiment and 1 gained Laves phase metal negative thermal expansion material of reference examples The stress-strain of Young's modulus (E) and the wide warm area negative expansion Laves phase alloy of 4 gained of embodiment is bent at room temperature Line.
Specific embodiment
A kind of wide warm area negative expansion Laves phase alloy proposed by the present invention, general formula Hf1-x-yZryTaxFe2, wherein 0.1≤x≤0.13,0≤y≤0.2.
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
11.17g iron block, 16.06gHf stick (purity 99.9%), 1.81gTa piece is weighed according to stoichiometric ratio to be placed on It in copper crucible, carries out electric arc melting 6 times under an argon atmosphere, ingot casting is stirred once after the completion of each electric arc melting, is then existed It anneals under vacuum condition, annealing temperature is 1100 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.9Ta0.1Fe2。
Embodiment 2
11.17g iron block, 15.88g Hf stick (purity 99.9%), 1.99gTa piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 8 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting It anneals under vacuum conditions, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.89Ta0.11Fe2。
Embodiment 3
11.17g iron block, 15.71g Hf stick (purity 99.9%), 2.17g Ta piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 7 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting Ingot casting after electric arc melting is placed in quartz ampoule, quartz ampoule is evacuated to vacuum and is sealed, sealed silica envelope is placed in case It anneals in formula resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.88Ta0.12Fe2。
Embodiment 4
11.17g iron block, 15.53gHf stick (purity 99.9%), 2.35gTa piece is weighed according to stoichiometric ratio to be placed on It in copper crucible, carries out electric arc melting 6 times, stirs ingot casting once under an argon atmosphere after the completion of each electric arc melting, then will Ingot casting after electric arc melting is placed in quartz ampoule, and quartz ampoule is evacuated to vacuum and is sealed, and sealed silica envelope is placed in box It anneals in resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.87Ta0.13Fe2。
Embodiment 5
According to stoichiometric ratio weigh 11.17g iron block, 14.28gHf stick (purity 99.9%), 1.81gTa piece, 0.91gZr particle is placed in copper crucible, is carried out electric arc melting 6 times under an argon atmosphere, will casting after the completion of each electric arc melting Ingot stirs once, and then the ingot casting after electric arc melting is placed in quartz ampoule, and quartz ampoule is evacuated to vacuum and is sealed, and will seal Quartz ampoule is placed in chamber type electric resistance furnace and anneals, and annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.8Zr0.1Ta0.1Fe2。
Embodiment 6
According to stoichiometric ratio weigh 11.17g iron block, 12.49gHf stick (purity 99.9%), 1.81g Ta piece, 1.82gZr particle is placed in copper crucible, is carried out electric arc melting 6 times under an argon atmosphere, will casting after the completion of each electric arc melting Ingot stirs once, and then the ingot casting after electric arc melting is placed in quartz ampoule, and quartz ampoule is evacuated to vacuum and is sealed, and will seal Quartz ampoule is placed in chamber type electric resistance furnace and anneals, and annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.7Zr0.2Ta0.1Fe2。
Embodiment 7
According to stoichiometric ratio weigh 11.17g iron block, 12.49g Hf stick (purity 99.9%), 2.17gTa piece, 1.64gZr particle is placed in copper crucible, is carried out electric arc melting 6 times under an argon atmosphere, will casting after the completion of each electric arc melting Ingot stirs once, and then the ingot casting after electric arc melting is placed in quartz ampoule, and quartz ampoule is evacuated to vacuum and is sealed, and will seal Quartz ampoule is placed in chamber type electric resistance furnace and anneals, and annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.7Zr0.18Ta0.12Fe2。
Embodiment 8
According to stoichiometric ratio weigh 11.17g iron block, 11.96gHf stick (purity 99.9%), 2.35gTa piece, 1.82gZr particle is placed in copper crucible, is carried out electric arc melting 6 times under an argon atmosphere, will casting after the completion of each electric arc melting Ingot stirs once, and then the ingot casting after electric arc melting is placed in quartz ampoule, and quartz ampoule is evacuated to vacuum and is sealed, and will seal Quartz ampoule is placed in chamber type electric resistance furnace and anneals, and annealing temperature is 900 DEG C, and annealing time is 7 days, obtains wide warm area negative expansion Laves phase alloy Hf0.67Zr0.2Ta0.13Fe2。
Embodiment 9
According to stoichiometric ratio weigh 11.17g iron block, 15.53g Hf stick (purity 99.4%, it is miscellaneous containing 0.6%Zr Matter), 2.35gTa piece be placed in copper crucible, carry out electric arc melting 6 times under an argon atmosphere, will after the completion of each electric arc melting Ingot casting stirs once, and then the ingot casting after electric arc melting is placed in quartz ampoule, and quartz ampoule is evacuated to vacuum and is sealed, will be close Envelope quartz ampoule, which is placed in chamber type electric resistance furnace, anneals, and annealing temperature is 900 DEG C, and annealing time is 7 days, and it is swollen to obtain the negative heat of wide warm area Swollen Laves phase alloy Hf0.86Zr0.01Ta0.13Fe2。
Reference examples 1
11.17g iron block, 15.35g Hf stick (purity 99.9%), 2.53gTa piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 6 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting Ingot casting after electric arc melting is placed in quartz ampoule, quartz ampoule is evacuated to vacuum and is sealed, sealed silica envelope is placed in case It anneals in formula resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains Laves phase metal negative thermal expansion material Hf0.86Ta0.14Fe2。
Reference examples 2
11.17g iron block, 14.99g Hf stick (purity 99.9%), 2.90gTa piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 6 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting Ingot casting after electric arc melting is placed in quartz ampoule, quartz ampoule is evacuated to vacuum and is sealed, sealed silica envelope is placed in case It anneals in formula resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains Laves phase metal negative thermal expansion material Hf0.84Ta0.16Fe2。
Reference examples 3
11.17g iron block, 14.64g Hf stick (purity 99.9%), 3.26gTa piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 6 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting Ingot casting after electric arc melting is placed in quartz ampoule, quartz ampoule is evacuated to vacuum and is sealed, sealed silica envelope is placed in case It anneals in formula resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains Laves phase metal negative thermal expansion material Hf0.82Ta0.18Fe2。
Reference examples 4
11.17g iron block, 14.28g Hf stick (purity 99.9%), 3.62gTa piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 6 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting Ingot casting after electric arc melting is placed in quartz ampoule, quartz ampoule is evacuated to vacuum and is sealed, sealed silica envelope is placed in case It anneals in formula resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains area Laves phase metal negative thermal expansion material Hf0.8Ta0.2Fe2。
Reference examples 5
11.17g iron block, 13.39g Hf stick (purity 99.9%), 4.52gTa piece is weighed according to stoichiometric ratio to place It in copper crucible, carries out electric arc melting 6 times, stirs ingot casting once, then under an argon atmosphere after the completion of each electric arc melting Ingot casting after electric arc melting is placed in quartz ampoule, quartz ampoule is evacuated to vacuum and is sealed, sealed silica envelope is placed in case It anneals in formula resistance furnace, annealing temperature is 900 DEG C, and annealing time is 7 days, obtains Laves phase metal negative thermal expansion material Hf0.75Ta0.25Fe2。
Hf stick purity is mass percent in specific embodiment, if purity is 99.9%, indicates the quality of Hf in Hf stick Score is 99.9%.
Width warm area negative expansion Laves phase alloy made from embodiment 1,3,4 and reference examples 1-5 gained Laves phase metal It is as shown in Figure 1 that the linear thermal expansion (Δ L/L) of negative thermal expansion material varies with temperature curve.
It will be seen from figure 1 that for material Hf1-xTaxFe2, when the Ta amount of mixing x=0.1 (embodiment 1), material exists NTE, Δ T=69K (283K-352K), α are shown in 287K-356K warm areaL=-10.7ppm/K.When the Ta amount of mixing x increases to When 0.12 (embodiment 3), NTE warm area (250K-337K) broadening, Δ T=87K, αLIt is reduced to -14.4ppm/K.And when Ta mixes When amount x increases to 0.13 (embodiment 4), NTE warm area (222K-327K) is further broadened, Δ T=105K, αLBe reduced to- 16.3ppm/K, wherein close to linear NTE warm area (277K-327K), Δ T=50K, αLReachable -29.3ppm/K is averaged Negative expansion coefficient numerical value is commercial NTE material ZrW2O8More than 3 times of (α=- 9ppm/K) are even greater than known as high thermal expansion system Several metal material Al (α=23ppm/K at room temperature).However, (the reference examples 1-5, although lattice is received after the Ta amount of mixing x > 0.14 The magnitude of contracting increases, and NTE warm area does not continue to but broaden.For the Ta amount of mixing x=0.18 (reference examples 3) and the Ta amount of mixing x= The sample of 0.2 (reference examples 4), Δ L/L show sharp keen transformation near 197K and 137K respectively, and the Ta amount of mixing x= This sharp keen transformation of 0.25 sample has disappeared, and all shows positive swelling properties in entire warm area.As it can be seen that as the amount of mixing x When=0.13, Hf1-xTaxFe2Material shows optimal NTE characteristic, and with biggish Lattice Contraction and wider NTE temperature Area, can be comparable with other metal NTE materials at room temperature, for example, it has been reported that the compound for the anti-perovskite structure crossed Ga0.7Ge0.3N0.88C0.12Mn3In 197-319K (Δ T=122K) warm area αLFor -18ppm/K, fine grain GaNMn3In 250K- 360K (Δ T=110K) warm area αLFor -21.5ppm/K, LaFe10.5Co1.0Si1.5In 240Kand350K (Δ T=110K) warm area αLFor -26.1ppm/K.
To the wide warm area negative expansion Laves phase alloy Hf of 3 gained of embodiment0.88Ta0.12Fe2It carries out from the 110K to 450K Alternating temperature XRD measurement, the lattice parameter (Volume and Lattice constant) of material varies with temperature relationship such as Fig. 2 institute Show.
Figure it is seen that in entirely measurement warm area, Hf0.88Ta0.12Fe2Material does not have the change of lattice symmetry.? Phase transition temperature TCUnder, a and b show NTE, and c is then shown as PTE, and in 250-340K warm area, Hf0.88Ta0.12Fe2Material The coefficient of volume expansion α of materialV=45.5ppm/K (αL~αV/3=-15.2ppm/K), it is consistent with strain-gauge test.
Measure Ha made from embodiment 5 and 60.9-yZryTa0.1Fe2The hot expansion property of compound, the linear heat of material Expansion (Δ L/L) varies with temperature curve and average linear thermal expansion (αL) size and corresponding warm area it is as shown in Figure 3.
From figure 3, it can be seen that for Ha0.9-yZryTa0.1Fe2(0≤y≤0.2) material, αLAbsolute value adulterate with Zr The increase of amount y is slowly increased, and NTE warm area temperature difference T is broadened to low temperature significantly.For y=0.2, (purity of Hf is equivalent to 77.8%), Δ T is up to 112K (240K-352K), and when the purity of Hf drops to 99.5% from 99.9%, its price drops An order of magnitude.Above-mentioned the results show selects the lower Hf metal of purity to prepare NTE material Hf1-x-yZryTaxFe2More Economical and effective.
In actual application, for NTE material other than the requirement of negative expansion performance, for material it is thermally conductive, Electric conductivity and mechanical performance requirement equally with higher.Therefore, inventor measures embodiment 1 in the present invention, embodiment 4 It the thermal conductivity of 4 gained Laves phase metal negative thermal expansion material of the wide warm area negative expansion Laves phase alloy of gained and reference examples and leads Electric rate, the thermal conductivity (k) of three kinds of materials vary with temperature curve and conductivity (σ) to vary with temperature curve as shown in Figure 4.
It can be seen that from Fig. 4 (a) under room temperature, as the gained Hf of the Ta amount of mixing x=0.1,0.13 and 0.21-xTaxFe2Material The thermal conductivity k value of material is respectively 10.5W (mK)-1、10.1W·(m·K)-1With 9.6W (mK)-1, it is commercial NTE material Expect ZrW2O8(k=0.5W (mK)-1) more than 20 times, and be greater than other NTE materials, such as typical metal NTE material LaFe10.5Co1.0Si1.5K value at room temperature is 6W (mK)-1, Cu0.6Si0.05Ge0.35NMn3For 3.7W (mK)-1, Mn0.98CoGe is 7W (mK)-1。
It can be seen that from such as Fig. 4 (b) under room temperature, as the gained Hf of the Ta amount of mixing x=0.1,0.13 and 0.21-xTaxFe2 The conductivityσ of material reduces as temperature increases, and shows the feature of metal.As the Ta amount of mixing x=0.1,0.13 and 0.2 When, Hf1-xTaxFe2Conductivityσ's value of material is respectively 1.18MS/m, 1.08MS/m and 0.96MS/m.This σ value is close to commercialization 36 alloy of invar (1.19MS/m), but be far longer than it has been reported that metal NTE material, such as LaFe10.5Co1.0Si1.5 (0.62MS/m)、Cu0.6Si0.05Ge0.35NMn3(0.29MS/m).In addition to thermal expansion coefficient (Coefficient of can be inhibited Thermal Expansion, CTE) outside, Hf1-xTaxFe2The heat that high heat conductance can be subject in thermal cycle with lightening material is answered Power has very big advantage in practical applications.In addition, good thermal conductive property can to avoid connection microdevice due to office Performance degradation caused by portion generates heat.
To embodiment 1, embodiment 3, the wide warm area negative expansion Laves phase alloy of 4 gained of embodiment and reference examples 1, control 2 gained Laves phase metal negative thermal expansion material of example has carried out Mechanics Performance Testing at room temperature, wherein embodiment 1, reality It is negative to apply example 3, the wide warm area negative expansion Laves phase alloy of 4 gained of embodiment and reference examples 1,2 gained Laves phase metal of reference examples Shown in the hardness of thermal expansion material such as Fig. 5 (a)；Embodiment 1, embodiment 3, the wide warm area negative expansion Laves phase of 4 gained of embodiment The Young's modulus (E) of 1 gained Laves phase metal negative thermal expansion material of alloy and reference examples is such as shown in Fig. 5 (b)；4 gained of embodiment Shown in load-deformation curve such as Fig. 5 (b) of wide warm area negative expansion Laves phase alloy.
It can be seen that at room temperature from Fig. 5 (a), as the Ta amount of mixing x=0.1,0.13 and 0.2, Hf1-xTaxFe2 The Vickers hardness of material is above 850Hv, and as the Ta amount of mixing x=0.13, Vickers hardness is 882HV, the Ta amount of mixing x=0.12 When Vickers hardness 904HV.So high hardness has been more than most metals material, such as the Fe-Ni invar alloy (dimension of Fe-36Ni Family name's hardness is 150-200Hv) and others NTE material (such as Cu0.5Ge0.5NMn3Vickers hardness be 400Hv).
It can be seen that at room temperature from Fig. 5 (b), as the Ta amount of mixing x=0.1,0.13 and 0.2, Hf1-xTaxFe2 The Young's modulus of material is above 200GPa, and being far longer than most metals material, (such as Cu is 117GPa, Al 69GPa, Ti are 110GPa) and invar alloy (137~145GPa).In addition, Hf1-xTaxFe2Material also has very high compression strength, such as works as Ta When the amount of mixing x=0.13, Hf1-xTaxFe2The compression strength of material is 382MPa.
It can be seen that Hf from above-mentioned performance test data1-xTaxFe2Material have biggish Vickers hardness, Young's modulus with And compression strength, make the material in PTE Application of composite have many advantages.The CTE of composite material be not simply by The different proportion of PTE and NTE calculates, and has significant ground relationship with the bulk modulus of component.In general, harder component pair The CTE of composite material has bigger influence, this is because they can be such that other components deform and this in material telescopic process Body is not easy deformation.In NTE material, biggish bulk modulus means that less additional amount can compensate basis material PTE.This is most important to simple, light weight composite material is designed.Furthermore Hf1-xTaxFe2The good engineering properties of material is in addition to adjusting Control CTE can also enhance the performance of PTE basis material.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (8)

1. a kind of width warm area negative expansion Laves phase alloy, which is characterized in that general formula Hf1-x-yZryTaxFe2, wherein 0.1≤ X≤0.13,0≤y≤0.2.
2. wide warm area negative expansion Laves phase alloy according to claim 1, which is characterized in that the negative heat of width warm area is swollen Swollen Laves phase alloy is in T1~T2Negative expansion property, 222K≤T are shown in warm area1≤ 287K, 327K≤T2≤ 356K is born The temperature difference T for thermally expanding warm area is 69K~112K.
3. width warm area negative expansion Laves phase alloy according to claim 1 or claim 2, which is characterized in that the negative heat of width warm area Expand the average linear coefficient of expansion α of Laves phase alloyLFor -10.7~-16.3ppm/K.
4. wide warm area negative expansion Laves phase alloy according to claim 1, which is characterized in that work as x=0.13, when y=0, Obtain wide warm area negative expansion Laves phase alloy Hf0.87Ta0.13Fe2In the average linear coefficient of expansion α of warm area 277K~327KL For -29.3ppm/K.
5. any one of -4 wide warm area negative expansion Laves phase alloy according to claim 1, which is characterized in that the wide temperature Zr in area's negative expansion Laves phase alloy is from impurities Zr in raw material Hf metal.
6. a kind of preparation method of warm area negative expansion Laves phase alloy wide as described in claim any one of 1-5, feature exist In including the following steps: according to Fe, Hf, Ta, Zr in Hf1-x-yZryTaxFe2In stoichiometric ratio weigh raw material, be placed in argon gas Electric arc melting is carried out under atmosphere, is then annealed under vacuum conditions, and annealing temperature is 900-1100 DEG C, and it is negative to obtain the wide warm area Thermally expand Laves phase alloy.
7. the preparation method of width warm area negative expansion Laves phase alloy according to claim 6, which is characterized in that annealing Temperature is 1000 DEG C, and annealing time is 7 days.
8. the preparation method of width warm area negative expansion Laves phase alloy according to claim 6 or 7, which is characterized in that electricity Arc melting more than six times, is stirred ingot casting once after the completion of each electric arc melting.
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