CN100354448C - Cu base Cu-Zr-Ti group block non-crystal alloy - Google Patents
Cu base Cu-Zr-Ti group block non-crystal alloy Download PDFInfo
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- CN100354448C CN100354448C CNB200410020899XA CN200410020899A CN100354448C CN 100354448 C CN100354448 C CN 100354448C CN B200410020899X A CNB200410020899X A CN B200410020899XA CN 200410020899 A CN200410020899 A CN 200410020899A CN 100354448 C CN100354448 C CN 100354448C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 37
- 239000000956 alloy Substances 0.000 title claims abstract description 37
- 239000013078 crystal Substances 0.000 title description 6
- 239000010949 copper Substances 0.000 claims abstract description 134
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 47
- 238000002844 melting Methods 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005266 casting Methods 0.000 claims abstract description 19
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 48
- 230000008018 melting Effects 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 12
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 229910004356 Ti Raw Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910017985 Cu—Zr Inorganic materials 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 238000007496 glass forming Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 28
- 239000005300 metallic glass Substances 0.000 description 28
- 238000001816 cooling Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 229910003126 Zr–Ni Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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Abstract
The present invention relates to a bulk amorphous alloy of Cu based Cu-Zr-Ti in the new material field, which comprises a Cu element, a Zr element and a Ti element. The present invention is characterized in that an alloy general formula is (Cu<x>Zr<1-x>) <1-y>Ti<y>, wherein the x is larger than or equal to 54 at. % and is smaller than or equal to 70 at. %, and the y is larger than or equal to 2 at. % and is smaller than or equal to 20 at. %. An optimum amorphous component is Cu<64>Zr<28.5>Ti<7.5>. The steps of a preparation process are characterized in that the non-consumable arc-melting of auxiliary materials and alloy ingots and the copper mould negative pressure suction casting of a bulk amorphous alloy are adopted. The gas pressure of argon is 0.03 (+/-) 0.01MPa, current density is 150 (+/-) 10 A/cm<2>, and gas pressure difference is 0.01 (+/-) 0.005MPa. A bulk amorphous alloy with the diameter of 3mm is obtained. The present invention has the advantage that the proper amount of the element Ti is added in the suitable ingredient of Cu-Zr to effectively improve the thermal stability of an amorphous alloy, glass-forming ability and intensity.
Description
Technical field
The present invention relates to a kind of have large-amorphous forming capacity, the series bulk amorphous alloy of high-intensity Cu base Cu-Zr-Ti, belong to field of new.
Background technology
Amorphous metal alloy is the metal or alloy that a class has short range order, long-range disordered structure feature, and they have very high comprehensive mechanical property and unique physical and chemical performance.Yet because the influence of metal or alloy amorphous formation ability (promptly forming the ability of amorphous alloy) prepares the higher rate of cooling of such material require, general critical cooling rate is 10
5K/s.With cooling rate is preface from high to low, and chilling technique commonly used has: melt atomizing, film deposition techniques and copper roller chilling get rid of the band technology, and material shape often is low-dimensional materials such as powder, strip etc., and therefore its range of application is very limited.
Since earlier 1990s, headed by the Japan and the U.S., a series of alloying constituents have been found with strong amorphous formation ability, wherein be easy to the most make with the Zr base, its critical cooling rate is only in the 1K/s magnitude, can cast and method such as shrend is prepared into three-dimensional block materials with copper mold, be called as block amorphous alloy.Block amorphous alloy not only has more traditional low-dimensional non-crystaline amorphous metal more excellent machinery and physical and chemical performance, and simultaneously, owing to broken through the size constraint, they have the possibility as structured material.In addition, can realize accurate rapid shaping in this class material is between its supercooling liquid phase region, this favorable manufacturability can further have been expanded its range of application.At present, beautiful, day two countries are used for golf club and armor-piercing head with the Zr base block amorphous alloy, obtain enormous benefits.Recently, developed the base block amorphous system of multicomponent Cu abroad again, with respect to non-crystaline amorphous metals such as Zr base, Pd bases, Cu is base block amorphous to have higher intensity and cheap price, and more practical value is arranged.At present, known Cu base block amorphous alloy all is (can form the less bulk amorphous alloy of size except indivedual compositions in this system in Cu-Zr binary amorphous architectonical, most compositions only can form and get rid of the band amorphous) the basis on, new constituent element grows up by adding, as Cu-Zr-Al, Cu-Zr-Ti and Cu-Ti-Zr-Ni etc.
Inoue group utilizes copper mold casting to study the formation of Cu-Zr-Ti bulk amorphous alloy (but reference: A.Inoue, W.Zhang, T.Zhang and K.Kurosaka:Mater.Trans.JIM 42 (2001) 1149) at first, and they are with Cu
60Zr
40As initial composition, to add the 3rd constituent element Ti and substitute part Zr, interval steps is 10at.%.The thermostability of the non-crystaline amorphous metal that forms is (with glass transformation temperature T
gWith crystallization temperature T
xCharacterize) increase with Ti content and reduce; Composition is Cu preferably
60Zr
30Ti
10Also have some researchists to think Cu
60Zr
30Ti
10The crystal phase (but reference: J.Z.Jiang, J.Saida, H.Kato, T.Ohsuna and A.Inoue:Appl.Phys.Lett.82 (2003) 4041) that contains nanoscale in the block amorphous alloy.
Comprehensively above-mentioned, there are two deficiencies in prior art:
The one, do not determine amorphous component scope and optimization composition, this is owing to there is not clear and definite composition criterion to do guidance, can only use very big composition step-length (10at.%), and the Cu of binary basic ingredient
60Zr
40Select also to have very much randomness;
The 2nd, may contain nanocrystallinely in the prepared amorphous, prove that the amorphous formation ability of the composition of being reported is lower.
Consideration in view of these two aspects, " the sub-concentration of power transformation " criterion that utilization of the present invention is relevant with cluster forms the amorphous in the Cu-Zr-Ti system has carried out comprehensive careful research, determined that the amorphous of inhaling under the cast bar spare forms composition range, and obtained optimized amorphous formation composition.
Summary of the invention
The objective of the invention is to overcome 2 deficiencies of the existing series bulk amorphous alloy of Cu-Zr-Ti, the composition range that causes greatly at interval of branch uncertain, with the nanocrystalline weak amorphous formation ability that manifests of appearance, provide to have formation scope and optimal components high glass forming ability, the series bulk amorphous alloy of high-intensity Cu-Zr-Ti special proposition technical solution of the present invention.
Realize that design of the present invention is, utilize " power transformation sub-concentration " amorphous alloy component criterion relevant with cluster; An amount of the 3rd constituent element Ti that adds forms the reasonable component proportioning on selected binary Cu-Zr basic ingredient; Adopt high purity constituent element element; The substep melting; Utilize suction casting means to prepare non-crystaline amorphous metal, confirm composition range and optimal components.
The series bulk amorphous alloy of Cu base Cu-Zr-Ti proposed by the invention comprises Cu, Zr and Ti element, it is characterized in that:
(a) the composition general formula of the series bulk amorphous alloy of Cu base Cu-Zr-Ti is: (Cu
xZr
1-x)
1-yTi
y, wherein, the span of x is: 54at.%≤x≤70at.%; The span of y is: 2at.%≤y≤20at.%, and at.% represents atomic percent;
(b) the best amorphous formation composition in the body series is Cu
64Zr
28.5Ti
7.5
The preparation method of the series bulk amorphous alloy of Cu base Cu-Zr-Ti, comprise composition proportion weighing, melting and suction casting, it is characterized in that: proceed step by step is answered in melting, comprises that to Cu-Zr-Ti be the melting of alloy pig and the suction casting of Cu-Zr-Ti block amorphous alloy, and processing step is:
The first step is got the raw materials ready
According to the atomic percent in the design mix, convert weight percent wt.% to, take by weighing each constituent element value, stand-by, the purity requirement of Cu, Zr, Ti raw metal is more than 99%;
Second step, the melting of Cu base Cu-Zr-Ti alloy pig
The compound of Cu, Zr and Ti metal is placed in the water jacketed copper crucible of arc-melting furnace, adopts the non-consumable arc melting method under the protection of argon gas, to carry out melting, at first be evacuated to 10
-2Pa, charging into argon gas to air pressure then is 0.03 ± 0.01MPa, the span of control of melting current density is 150 ± 10A/cm
2, after the fusing, continuing 10 seconds of melting again, outage allows alloy be cooled to room temperature with copper crucible, then with its upset, places again in the water jacketed copper crucible, carries out melting second time, and melt back like this at least 3 times obtains the uniform Cu-Zr-Ti alloy pig of composition;
The 3rd step, the preparation of Cu base Cu-Zr-Ti block amorphous alloy
The Cu-Zr-Ti alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, under argon shield,, at first be evacuated to 10 with non-consumable arc melting method molten alloy
-2Pa, charging into argon gas to air pressure then is 0.03 ± 0.01MPa, the used current density of melting is 150 ± 10A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.01 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm.
The solution of the present invention is that the power transformation sub-concentration line criterion relevant with cluster according to the multicomponent alloy phase designs amorphous alloy component.The sub-concentration line of so-called power transformation criterion refers to have in the binary subsystem special composition point of high glass forming ability, normally dark eutectic point or cluster constituent point, and the line between the 3rd constituent element.In this ternary system, Cu-Zr binary subsystem is that typical glass forms the eutectic system, can both obtain metallic glass by getting rid of the band method in the very wide composition range of rich Cu and poor Cu.People such as Altounian [Z.Altounian, G H.Tu and J.O.Strom-Olsen:J.Appl.Phys.53 (1982) 4775] point out from Cu
70Zr
30To Cu
55Zr
45Rich Cu metallic glass crystallization process in, oP-Cu
8Zr
3Phase (Cu
8Hf
3Type) and oC-Cu
10Zr
7Phase (Ni
10Zr
7Type) is the crystallization phase of separating out earlier.Cu
8Zr
3Be by Cu mutually
8Zr
5The icosahedron cluster is formed, and exists the icosahedron cluster to help forming in the non-crystaline amorphous metal and has high amorphous formation ability and thermostability non-crystaline amorphous metal; And Cu
10Zr
7Comprised Cu mutually
6Zr
5Cluster, i.e. anti-prismatic attached two and half octahedrons of Archimedes, it is that to describe the Bernal of amorphous structure polyhedral a kind of.From the Cu-Zr binary phase diagram as can be seen, Cu
8Zr
5(Cu
61.5Zr
38.5) and Cu
6Zr
5(Cu
54.5Zr
45.5) two dark eutectic points at corresponding rich Cu place respectively, Cu
61.8Zr
38.2And Cu
56Zr
44In addition, at hp-Cu
51Zr
14Phase (Ag
51Gd
14Type) also there is another icosahedron cluster Cu in
9Zr
4But, its not corresponding any eutectic point.These three clusters all are to be the center with little atom Cu, and are positioned at the right side of its parent phase, have increased dissimilar interatomic ligancy.Buschow [Journal of Applied Physics, v52, n5, May, 1981, p3319-3323] is to Zr
1-xCu
xBinary metal glass carries out finding behind the crystallization dynamics research, and crystallization intensity of activation (Δ E) occurs three extreme values at x=0.56,0.62 with the office that becomes of 0.67 rich Cu.Just, these three special clusters, Cu
6Zr
5, Cu
8Zr
5And Cu
9Zr
4, respectively corresponding these three special composition.Though x=0.67 becomes the not corresponding two component eutectic point in office, Δ E has produced maximum value near this composition.The composition alloy that Δ E produces extreme value has intensive chemistry short range order.Therefore, the present invention has chosen this three special composition Cu
56Zr
44, Cu
61.8Zr
38.2And Cu
9Zr
4, connect the 3rd constituent element Ti respectively and just obtain three sub-concentration lines of power transformation: (Cu
56Zr
44)
1-xTi
x, (Cu
61.8Zr
38.2)
1-xTi
x(Cu
9Zr
4)
1-xTi
x
These compositions have overcome the main drawback of prior art, divide the randomness choose and big composition at interval, carried out determining and optimizing of amorphous component scope.
Adopting non-consumable arc-melting furnace and copper mold negative pressure suction casting machine to prepare Cu-Zr-Ti is non-crystaline amorphous metal.With X-ray diffractometer (SHIMADZU XRD-6000), differential scanning calorimeter (Mettler DSC822
e) and differential thermal analyzer (Mettler TGA/SDTA851
e) to analyze and measure Cu-Zr-Ti be the structure and the thermodynamical coordinate of alloy.Determine and inhale cast to become the composition range of 3mm diameter bar amorphous be (Cu
xZr
1-x)
1-yTi
y, wherein the x span is 54at.%≤x≤70at.%, and the y span is 2at.%≤y≤20at.%, and Cu
64Zr
28.5Ti
7.5Has maximum amorphous formation ability.
The X-ray diffraction result of Cu-Zr-Ti alloy shows, if Ti content is during less than 2at.% or greater than 20at.%, a large amount of bright and sharp diffraction peaks will appear in the X-ray diffraction spectrum of alloy, show and generated a large amount of crystal phases in the alloy, and when the Ti content in the alloy is in 3at.% to 20at.% scope, the X-ray diffraction spectrum of alloy bar all presents typical non-crystalline state diffractive features, shows that they are block amorphous alloys.Finally, experiment is determined: at (Cu
xZr
1-x)
1-yTi
y(54at.%≤x≤70at.%; In the composition range of 2at.%≤y≤20at.%), all can obtain the non-crystal bar of diameter 3mm by copper mold casting.Listed representational (Cu in the table 1
9Zr
4)
1-xTi
xThe relevant amorphous stability of series bulk amorphous alloy and the experimental data of formation ability.
T
g, T
xBe the characteristic parameter that characterizes the non-crystaline amorphous metal thermostability, its value increase shows the anti-crystallization ability reinforcement of amorphous, and the thermostability of amorphous is increasing.Table 1 shows that along with a small amount of (in 7.5～15at.% scope) of Ti element adds, Cu-Zr-Ti is that the thermostability dullness of non-crystaline amorphous metal reduces.Wherein, the non-crystaline amorphous metal with optimal heat stability is Cu
64Zr
28.5Ti
7.5, its T
g=736K, T
x=769K; Be higher than the best non-crystaline amorphous metal Cu that has reported
60Zr
30Ti
10Value, T
g=710K, T
x=739K.
Reduction glass transformation temperature T
Rg=T
g/ T
lIt is the significant parameter that characterizes amorphous formation ability.As can be seen from Table 1, T
RgIncrease the trend that also presents reduction with Ti, because Ti content is the T of the non-crystaline amorphous metal of 7.5at.%
gBe worth higherly, correspondingly, its reduction glass transformation temperature is bigger, T
g/ T
lBe 0.627.Similarly, at the parameter γ (γ=T of the sign amorphous formation ability that proposes recently
x/ (T
g+ T
l) the value aspect, Ti content is that the non-crystaline amorphous metal of 7.5at.% also has maximum value 0.403.Therefore, Cu
64Zr
28.5Ti
7.5Non-crystaline amorphous metal also has maximum amorphous formation ability, is better than Cu
60Zr
30Ti
10Glass forming ability, its T
g/ T
l=0.610, γ=0.394.
The test of room temperature density and hardness finds that the series bulk amorphous alloy density of Cu-Zr-Ti is close, but their vickers hardness number is along with the content generation obvious variation of Ti.When Ti content in the alloy when 7.5at.% is increased to 15at.%, the Vickers' hardness of block amorphous alloy is reduced to 5.66GPa from 6.74GPa.Wherein, Cu
64Zr
28.5Ti
7.5The hardness value of non-crystaline amorphous metal is the highest, is Hv=6.74GPa, is higher than the Cu of report
60Zr
30Ti
10Hardness value (Hv=6.51GPa measures under same test conditions).Formula σ rule of thumb
y=3Hv can estimate the yield strength of alloy, all above 1.7GPa, and the yield strength apparently higher than about the 1.5GPa of Zr base noncrystal alloy.
By above-mentioned experimental analysis, can draw following result: amorphous alloy component design method and preparation method by the present invention proposes, can carry out the optimizing components that Cu-Zr-Ti is a non-crystaline amorphous metal; The amorphous formation ability of the Ti element an amount of interpolation in appropriate C u-Zr composition effectively raising Cu-Zr base alloy, general, can only obtain amorphous by getting rid of band in the Cu-Zr two component system, its critical cooling rate is about 10
5～10
6The K/s magnitude.Because (7.5～15at.%) interpolation is at (the Cu of Cu-Zr-Ti alloy system for a small amount of Ti
xZr
1-x)
1-yTi
y(54at.%≤x≤70at.%; In the composition range of 2at.%≤y≤20at.%), all can obtain the non-crystal bar of diameter 3mm by copper mold casting, by experimental formula T
c(K/s)=10/R
2(cm) (T
cBe critical cooling velocity, R is that the maximum of non-crystaline amorphous metal forms thickness) can estimate that to form Cu-Zr-Ti be that the critical cooling velocity of non-crystaline amorphous metal is 10
2～10
3The K/s magnitude, than low 2～3 orders of magnitude of the critical cooling rate that forms the Cu-Zr non-crystaline amorphous metal, this shows that an amount of interpolation of Ti has improved more than 100 times the amorphous formation ability of Cu-Zr alloy.
Need to prove that material purity must reach more than 99%; Whole melting and suction casting process must be extracted into high back of the body end vacuum (at least 10
-2Pa) charge into after under the argon shield and carry out, to avoid oxidation; Melt the used current density of alloy involved in the present invention and be controlled at 150 ± 10A/cm
2, the excessive melting loss of elements that causes, too small can not the fusing; Melting at least 3 times, even to guarantee composition; Draught head will reach 0.01 ± 0.005MPa when negative pressure was inhaled casting, should guarantee viscous melt is sucked copper mold, again can not be too quickly, avoid producing pore.
General formula composition proposed by the invention all can adopt identical processing parameter to be prepared into the non-crystaline amorphous metal rod of 3mm diameter.
Advantage of the present invention is: 1. owing to an amount of adding of element ti, effectively raise the amorphous formation ability of Cu-Zr alloy, at (Cu
xZr
1-x)
1-yTi
y(wherein, the value of x is: 54at.%≤x≤70at.%; The value of y is: in the scope of 2at.%≤y≤20at.%), all available common copper mold casting is prepared the Cu-Zr-Ti non-crystaline amorphous metal rod that diameter is 3mm, and its critical cooling velocity that forms amorphous is 10
2～10
3The K/s magnitude, low 2～3 orders of magnitude of critical cooling rate than Cu-Zr non-crystaline amorphous metal show that the interpolation of Ti has improved more than 100 times the amorphous formation ability of Cu-Zr alloy; 2. because based on the guidance of the composition criterion of Binary Clusters, be able to determine that best amorphous component is Cu inhaling under the casting 3mm rod spare
64Zr
28.5Ti
7.5, its T
g=736K, T
x=769K, reduction glass transformation temperature T
g/ T
lBe 0.627, amorphous formation ability parameter γ (γ=T
x/ (T
g+ T
l)=0.403; 3. because Ti is again the effective element of reinforced alloys simultaneously, therefore, Cu base Cu-Zr-Ti block amorphous alloy all has high mechanical property, and its room temperature Vickers hardness surpasses 5.70GPa, rule of thumb formula σ
yThe yield strength that=3Hv estimates surpasses 1.7GPa.
The subordinate list explanation
Table 1 is the typical composition and the characteristic temperature measuring result of Cu-Zr-Ti block amorphous alloy.T
gThe expression second-order transition temperature, T
xCrystallization temperature, supercooling liquid phase region Δ T
x, T
lLiquidus point, T
g/ T
lThe reduction glass transformation temperature, parameter γ is defined as: T
x/ (T
g+ T
l).All non-crystaline amorphous metals (comprise and are used for correlated known Cu
60Zr
30Ti
10) all adopt identical processing method to prepare.The result shows: the series bulk amorphous alloy of Cu-Zr-Ti all has high thermostability and strong amorphous formation ability.Wherein, having optimal heat non-crystaline amorphous metal stable and amorphous formation ability is Cu
64Zr
28.5Ti
7.5, in table with "
*" number mark, its every index all is better than known Cu
60Zr
30Ti
10Non-crystaline amorphous metal shows that the present invention has optimized the amorphous component of this system.
Table 2 is the series bulk amorphous alloy at room temperature density of Cu-Zr-Ti p, hardness Hv and yield strength σ
yValue.All non-crystaline amorphous metals (comprise and are used for correlated known Cu
60Zr
30Ti
10) all adopt identical processing method to prepare.The result shows: the series bulk amorphous alloy of Cu-Zr-Ti all has higher hardness and intensity.Wherein, Cu
64Zr
28.5Ti
7.5Vickers hardness number be 6.74GPa, be higher than the best amorphous Cu that has reported
60Zr
30Ti
10, its vickers hardness number is 6.51GPa.
Embodiment
Below in conjunction with subordinate list, describe the embodiment of the series bulk amorphous alloy of Cu-Zr-Ti in detail, now have Cu with best amorphous formation ability
64Zr
28.5Ti
7.5Be example, the preparation process of the series bulk amorphous alloy of Cu-Zr-Ti is described.And, series bulk amorphous thermodynamics characteristics and the performance characteristic of Cu base Cu-Zr-Ti is described in conjunction with subordinate list.
Embodiment uses Cu
64Zr
28.5Ti
7.5Composition prepares block amorphous alloy
The first step, the weighing of composition proportion
Undertaken by atomic percent during design mix, in the raw material weighing process, earlier with alloy atom per-cent Cu
64Zr
28.5Ti
7.5Convert weight percent Cu to
57.9Zr
37.0Ti
5.1, the purity of weighing is 99.9% pure metal Zr in proportion, Ti and Cu raw material;
Second step, Cu
64Zr
28.5Ti
7.5The melting of alloy pig
With Cu, Zr, Ti metal mixed material, adopt the non-consumable arc melting method under the protection of argon gas, to carry out melting, at first be evacuated to 10
-2Pa, charging into argon gas to air pressure then is 0.03 ± 0.01MPa, the span of control of melting current density is 150 ± 10A/cm
2, after the fusing, continuing 10 seconds of melting again, outage allows alloy be cooled to room temperature with copper crucible, then with its upset, places again in the water jacketed copper crucible, carries out melting second time, and melt back like this 3 times obtains the uniform Cu of composition
64Zr
28.5Ti
7.5Alloy pig;
The 3rd step, Cu
64Zr
28.5Ti
7.5The block amorphous alloy preparation
With Cu
64Zr
28.5Ti
7.5Alloy pig places in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, with non-consumable arc melting method molten alloy, at first is evacuated to 10 under argon shield
-2Pa, charging into argon gas to air pressure then is 0.03 ± 0.01MPa, the used current density of melting is 150 ± 10A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.01 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm;
The 4th step, structure and performance test
With X-ray diffractometer (Cu K α radiation, its wavelength X=0.15406nm) is analyzed the phase structure of alloy bar, the diffractive features that presents typical amorphous structure of its X-ray diffraction spectrum shows it is non-crystaline amorphous metal, does not contain the crystal phase.
Measure the thermodynamical coordinate of this series alloy with differential scanning calorimeter and differential thermal analyzer, obtained its second-order transition temperature T
g(736K), crystallization temperature T
x(769K),, reduction glass transformation temperature T
g/ T
l(0.627) and characterize the parameter γ (0.403) of amorphous formation ability.It the results are shown in table 1.Relatively as seen, the amorphous formation ability of these non-crystaline amorphous metals is better than other non-crystaline amorphous metal in this system, comprises known with reference to composition Cu
60Zr
30Ti
10(sample all makes with under the similarity condition), so Cu
64Zr
28.5Ti
7.5Thermostability and the highest amorphous formation ability with body series the best.
Further vickers microhardness test shows, the body series optimal heat stability and the non-crystaline amorphous metal Cu of high amorphous formation ability
64Zr
28.5Ti
7.5Yield strength (2022MPa) and maximum density (7.76g/cm with the highest hardness (6.74GPa), maximum
3).
The typical composition and the characteristic temperature measuring result of table 1:Cu-Zr-Ti block amorphous alloy
| Composition(at％) | T g(K) | T x(K) | ΔT x(K) | T l(K) | T g/T l | γ |
| *Cu 64Zr 28.5Ti 7.5 Cu 62.3Zr 27.7Ti 10 Cu 60.6Zr 26.9Ti 12.5 Cu 58.8Zr 26.2Ti 15 Cu 60Zr 30Ti 10(with reference to composition) | 736 729 714 705 710 | 769 756 740 729 739 | 33 27 26 24 29 | 1173 1169 1140 1143 1163 | 0.627 0.624 0.626 0.617 0.610 | 0.403 0.398 0.399 0.394 0.394 |
"
*" number mark be the optimal heat stability and the alloying constituent of high amorphous formation ability
Room temperature density p, hardness Hv and the yield strength σ of table 2:Cu-Zr-Ti block amorphous alloy
yValue
| Composition(at％) | ρ(g/cm 3) | Hv(GPa) | σ y(MPa) |
| *Cu 64Zr 28.5Ti 7.5 Cu 62.3Zr 27.7Ti 10 Cu 60.6Zr 26.9Ti 12.5 Cu 58.8Zr 26.2Ti 15 Cu 60Zr 30Ti 10(with reference to composition) | 7.76 7.69 7.65 7.60 7.63 | 6.74 6.23 5.72 5.66 6.51 | 2022 1869 1716 1698 1953 |
"
*" number mark be the optimal heat stability and the alloying constituent of high amorphous formation ability
Claims (3)
1. based on the series bulk amorphous alloy of Cu base Cu-Zr-Ti of cluster, comprise Cu element, Ti element and Zr element, it is characterized in that: the series bulk amorphous alloy of Cu base Cu-Zr-Ti based on cluster is based on Cu
9Zr
4Cluster connects the sub-concentration line of the power transformation Cu of Ti
9Zr
4-Ti designs, and its composition expression formula is (Cu
9/13Zr
4/13)
100-xTi
x, x=7.5-15at.%.
2. the series bulk amorphous alloy of Cu base Cu-Zr-Ti based on cluster according to claim 1, it is characterized in that: it is Cu that the typical amorphous in the body series forms composition
64Zr
28.5Ti
7.5
3. prepare the preparation method of the series bulk amorphous alloy of Cu base Cu-Zr-Ti based on cluster as claimed in claim 1, comprise composition proportion weighing, melting and suction casting, it is characterized in that:
Proceed step by step is answered in melting, and processing step is:
The first step is got the raw materials ready
According to the atomic percent in the design mix, convert weight percent wt.% to, take by weighing each constituent element value, stand-by, the purity requirement of Cu, Zr, Ti raw metal is more than 99%;
Second step is based on the melting of the Cu of cluster base Cu-Zr-Ti alloy pig
The compound of Cu, Zr and Ti metal is placed in the water jacketed copper crucible of arc-melting furnace, adopts the non-consumable arc melting method under the protection of argon gas, to carry out melting, at first be evacuated to 10
-2Pa, charging into argon gas to air pressure then is 0.03 ± 0.01MPa, the span of control of melting current density is 150 ± 10A/cm
2, after the fusing, continuing 10 seconds of melting again, outage allows alloy be cooled to room temperature with copper crucible, then with its upset, places again in the water jacketed copper crucible, carries out melting second time, and melt back like this at least 3 times obtains the uniform Cu-Zr-Ti alloy pig of composition;
The 3rd step is based on the Cu base Cu-Zr-Ti block amorphous alloy preparation of cluster
The Cu-Zr-Ti alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, under argon shield,, at first be evacuated to 10 with non-consumable arc melting method molten alloy
-2Pa, charging into argon gas to air pressure then is 0.03 ± 0.01MPa, the used current density of melting is 150 ± 10A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.01 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm.
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| CN104232956A (en) * | 2014-09-26 | 2014-12-24 | 东莞台一盈拓科技股份有限公司 | Method for preparing copper-based amorphous alloy by using cold crucible smelting furnace device |
| CN106756132A (en) * | 2016-12-21 | 2017-05-31 | 重庆中鼎三正科技有限公司 | A kind of preparation method of Cu-Based bulk amorphous alloy |
| CN107385362A (en) * | 2017-07-10 | 2017-11-24 | 上海理工大学 | A kind of cu-base amorphous alloy silk with high-intensity high-tenacity and preparation method thereof |
| CN110499480A (en) * | 2019-09-30 | 2019-11-26 | 大连理工大学 | A kind of Cu-M-O amorphous alloy and preparation method thereof |
| CN111118414B (en) * | 2020-01-13 | 2021-10-08 | 江苏大学 | Method for preparing copper-based amorphous alloy from standard blister copper |
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