CN102108475A - Ti-based bulk metallic glass - Google Patents
Ti-based bulk metallic glass Download PDFInfo
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- CN102108475A CN102108475A CN 201010593926 CN201010593926A CN102108475A CN 102108475 A CN102108475 A CN 102108475A CN 201010593926 CN201010593926 CN 201010593926 CN 201010593926 A CN201010593926 A CN 201010593926A CN 102108475 A CN102108475 A CN 102108475A
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- 239000005300 metallic glass Substances 0.000 title abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000013461 design Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims description 64
- 239000010970 precious metal Substances 0.000 claims description 7
- 239000002419 bulk glass Substances 0.000 claims description 6
- 231100000614 poison Toxicity 0.000 claims description 4
- 230000007096 poisonous effect Effects 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 62
- 229910045601 alloy Inorganic materials 0.000 abstract description 60
- 238000000034 method Methods 0.000 abstract description 14
- 229910052802 copper Inorganic materials 0.000 abstract description 13
- 238000007496 glass forming Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 229910017755 Cu-Sn Inorganic materials 0.000 abstract description 3
- 229910017927 Cu—Sn Inorganic materials 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 231100000957 no side effect Toxicity 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 54
- 239000000470 constituent Substances 0.000 description 24
- 238000002844 melting Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910004353 Ti-Cu Inorganic materials 0.000 description 10
- 238000005275 alloying Methods 0.000 description 10
- 230000005496 eutectics Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- 229910018100 Ni-Sn Inorganic materials 0.000 description 4
- 229910018532 Ni—Sn Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910010165 TiCu Inorganic materials 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 229910015371 AuCu Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention relates to a piece of Ti-based bulk metallic glass, which belongs to the technical field of new materials. The invention is characterized in that the glass comprises Ti, Zr, Cu (or Ni), and Sn components; the glass forming ability is great, and toxic Be and expensive valuable metal components are not included; and Ti-Zr-Cu(-Ni)-Sn bulk metal glass series compositions are designed with the method similar to component replacement according to 'dual cluster plus amorphous design' quantitative criterion, and the typical compositions are as follows: Ti[60-50]Zr[3.0-7.5]Cu[21-32.5]Ni[18-7.0]Sn[2.0-4.0] and Ti[40.6]Zr[9.4]Cu[31.3-46.9]Ni[15.6-0]Sn[3.1] (atomic percentage). The invention has the effects and benefits as follows: (1) Ti-based bulk metallic glass with great forming ability is produced in the system excluding Be and Pd, and the critical dimension of the glass can reach 7mm; (2) multi-component alloy compositions are designed according to the 'dual cluster plus amorphous design' quantitative criterion, so that the problem of random selection on composite distribution can be solved among components of a complex alloy system; (3) Ti-Zr-Cu-Sn metallic glass alloy new system which has no side effects on human bodies is developed, and the glass is favorable for application to biomedicine.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of Ti bast block metal glass that does not contain the big glass forming ability of poisonous element Be and precious metal constituent element.
Background technology
Non-crystaline amorphous metal possesses short range order long-range disordered structure feature, has good comprehensive mechanical property and unique physical and chemical performance usually.General, the glass forming ability of alloy is relatively low, and (general critical cooling rate is 10 under higher cooling rate
5K/s), alloy liquid solidifies and just can avoid crystallization and form non-crystalline state.Therefore, early stage amorphous alloy material normally prepares by chilling technique (getting rid of band technology etc. as melt atomizing, film deposition techniques and copper roller chilling), is the powder or the silk ribbon shape of low-dimensional, and this has limited the application of amorphous alloy material greatly.
The eighties of last century the nineties begins, Japan and U.S. scientist have taken the lead in finding having the alloying constituent series of big glass forming ability, their alloy melt can solidify the non-crystaline amorphous metal that forms three-dimensional dimension, i.e. block metal glass by methods (critical speed of cooling can reach the 1K/s magnitude) under conventional cooling rate such as ordinary copper die cast and shrends.This block metal glass has been broken through the limitation of size of traditional low-dimensional non-crystaline amorphous metal, has expanded the non-crystaline amorphous metal range of application greatly, is expected to be applied in various fields as advanced material.In this simultaneously, block metal glass has good thermostability usually, the particularly existence of supercooling liquid phase region makes block metal glass be easy to realize (surpassing) precise forming in supercooling liquid phase region, and this characteristic has further been expanded the application space of bulk metallic glass materials.At present, states such as U.S., day developed Zr base, Pd base, Fe base, RE (rare earth) base, Ni is basic and block metal glass such as Cu base, and with part bulk metallic glass materials practicability, has obtained success.
Ti bast block metal glass alloy has low density, high strength, outstanding etch resistant properties and the characteristic of excellent biological compatibility, can be used as Structural Engineering material and biomedical material, is subjected to people's extensive concern.But less glass forming ability (GFA) has restricted Ti base metal glass Development of Materials and application greatly.Recently, the Inoue group of the Kim group of Korea S and Japan finds that metal Be and Pd can effectively improve the glass forming ability of Ti base alloy, the Ti bast block metal glass of the big GFA of concurrent exhibition, and its typical composition is respectively Ti
40Zr
25Ni
8Cu
9Be
18(critical size that amorphous forms is 18mm) and Ti
40Zr
10Cu
36-xPd
14Sn
xX
Sn=0-6 (its critical size is 10mm); But the high composition of the toxic side effect of Be and steam thereof and precious metals pd has restricted the development of these Ti base metal glass greatly.At present, how preparing large-sized metallic glass in not containing the Ti base alloy system of Be and precious metal is one of focus of Ti base metal glass research.For example, the great waves group of opening of Beijing Institute of Aeronautics prepares the bar-shaped sample that diameter is 3mm in Ti-Zr-Cu-Ni system; And in the Ti-Zr-Cu-Ni-Sn system, the alloy of the maximum glass forming ability of report can form the metallic glass rod of 5mm at present, and its composition is Ti
50Zr
5Cu
25Ni
15Sn
5, but, cause that repeatability is relatively poor as a result because its GFA is limited, under our preparation condition, the critical size of the formation amorphous of this alloy is no more than 3mm; In addition, the Ti-Zr-Cu-Ni-Sn alloy of other all reports, its critical size that forms glass all is lower than 4mm.
On the other hand, the block metal glass composition is generally multicomponent, complicated component.And, coach still lacking effective quantitative criteria aspect the block metal glass composition Design at present.Though people's such as experience three principles that the metallic glass of Japanese Inoue forms and U.S. Turnbull dark eutectic model scheduling theory provides direction for to a certain extent the selection of alloying constituent, but the composition of most of block metal glass is still realized screening by a large amount of experiments and is optimized, this has influenced alloy development efficiency greatly, and has caused big resource consumptions such as person property.
Present Research at the Ti bast block metal glass, the present invention's utilization " cluster+connection atom " structural models quantitative design and definite Ti-Zr-Cu (Ni)-Sn can form the alloy component range of bulk glass in being, and the Ti bast block metal glass alloy series with big glass forming ability that utilizes the copper mold technological development to make new advances.
Summary of the invention
The technical problem to be solved in the present invention is: 1. in the system that does not contain poisonous element (for example Be) and precious metal element (as Pd), develop the have bigger formation ability Ti bast block metal glass series of (critical size surpasses 5mm); 2. on becoming component selections and optimizing, overcome arbitrariness and numerous and diverse property of traditional trial and error method.In the present invention, we will adopt " two clusters+connection atom " structural models, be the base growth multicomponent system and shall carry out quantitative composition design with the Ti-Cu binary, select and determine to have the Ti bast block metal glass composition series of big formation ability.
The technical solution that the present invention adopts is: a kind of multicomponent Ti base metal glass, contain Ti, and Zr, Cu, Sn can contain the Ni constituent element, it is characterized in that:
(a) going out Ti Quito constituent element glass according to " two clusters+connection atom " structural models quantitative design and form alloying constituent, is Ti between concrete Composition Region
60-50Zr
3.0-7.5Cu
21-32.5Ni
18-7.0Sn
2.0-4.0And Ti
40.6Zr
9.4Cu
31.3-46.9Ni
15.6-0Sn
3.1(atomic percent) can obtain the bar-shaped block metal glass sample of different size.Ti wherein
40.6Zr
9.4Cu
37.5-40.6Ni
9.4-6.3Sn
3.1Becoming the glass formation critical size of office is 7mm, is the Ti base alloy that does not contain Be and precious metal constituent element of present GFA maximum.
(b) comprised the Ti base Ti-Zr-Cu-Sn bulk glass alloying constituent that does not contain Ni in the above-mentioned composition that forms bulk glass, can eliminate of the side effect of Ni element, had good biomedical applications prospect human body.
The design that realizes technique scheme is: utilizing us to develop " two clusters+connection atom " structural models voluntarily, to come quantitative design Ti-Zr-Cu-Ni-Sn be the glassy alloy composition." two clusters+connection atom " structural models had been based on before " cluster+connection atom " structural models development and had come, here " two cluster " stems from the Local Structure of the relevant phase of eutectic of basic two component eutectic point both sides, non-crystal structure is considered as the relevant two clusters of eutectic and separately the atomic building that is connected, in view of the above, can obtain the consisting of of alloy [cluster 1] (connecting atom 1) x}+{[cluster 2] (connecting atom 2) x}, the reduction empirical formula of alloy is [reduction cluster] (reduction connection atom) x, x is that (reduction) of each (reduction) cluster correspondence connects the atom number, according to alloy (reduction) empirical formula, but direct quantitative calculates the degree of each constituent element in the alloy.For satisfying the topological Mi Dui requirement of cluster stacking, the connection atom generally occupies octahedron or the tetrahedral interstice between cluster, like this, the connection atom number x of each cluster correspondence, general value 1 or 3 is (referring to Dong C, Wang Q, Qiang J B, et al, J.Appl.Phys.D, 2007,49:R273).
Be example now, the process of setting up of (reduction) empirical formula of Ti-Cu metallic glass alloys is described with the Ti-Cu foundational system among the present invention.In the Ti-Cu phasor, there is rich titanium eutectic point Ti
57Cu
43, the eutectic of its both sides is relevant to be TiCu phase (AuCu type) and Ti mutually
2Cu phase (MoSi
2Type), all existing in this two-phase with Cu is the Ti of the heart
8Cu
5The Local Structure cluster (be expressed as Cu-Cu4Ti8, "-" preceding expression cluster central atom, the back is the shell atom), but the close heap of two clusters is slightly different.Ti
57Cu
43Eutectic point can be expressed as with the cluster empirical formula:
Wherein, Cu is cluster the Cu-Cu4Ti8 (=Ti of the heart
8Cu
5) respectively from TiCu and Ti
2The Cu eutectic phase of being correlated with, connecting atom all is 1 Cu.The two component eutectic point is easily to form amorphous component, and it is the foundation stone that development multicomponent bulk glass forms system.With Ti
57Cu
43" two clusters+connection atom " structural models of eutectic point, i.e. [Cu-Cu4Ti8] Cu1+[Cu-Cu4Ti8] Cu1, be the basis, (similar according to approximate element such as atomic size, or chemical property is similar) the replacement principle, introduce alloy element in the structure of Ti-Cu binary basis " two clusters+connection atom ", the multicomponentization that realizes the Ti-Cu two component system is to improve the GFA of alloy.For example, we replace Ti with Zr, replace Cu with Ni, Sn removes to replace connection atom Cu:[Cu-Cu2Ni2Ti6Zr2 simultaneously] Ni1-[Cu-Cu3NiTi7Zr1] Sn1, in view of the above, obtain reduction cluster empirical formula with multicomponent alloy---[Cu-Cu2.5Ni1.5Ti6.5Zr1.5] is Ti46.4Zr10.6Cu28.6Ni10.7Sn3.6 but direct quantitative calculates the chemical constitution of this alloy (Ni0.5Sn0.5), experiment showed, that this one-tenth office can form the bulk glass rod of 4mm (participation subordinate list).Similarly, guaranteeing that Ti is under the prerequisite of matrix constituent element, by to shell in the structure of Ti-Cu binary basis " two clusters+connection atom " be connected substituting in various degree of former sub-component individuality, the Ti-Zr-Cu-Ni-Sn that we obtain that Ti content is in 50～60at.% is block metal glass composition series: Ti
60-50Zr
3.0-7.5Cu
21-32.5Ni
18-7.0Sn
2.0-4.0
Be the situation when connection atomicity x is 1 (being x=1) in Ti-Cu binary " two clusters+connection atom " model above, can successfully resolve the Ti57Cu43 eutectic point, and this go out Ti for base growth
60-50Zr
3.0-7.5Cu
21-32.5Ni
18-7.0Sn
2.0-4.0Block metal glass composition series.When connection atomicity x gets 3, to obtain the another kind of cluster expression formula of Ti-Cu binary " two clusters+connection atom " structural models: [Cu-Cu4Ti8] Cu3+[Cu-Cu4Ti8] Cu3, its reduction cluster empirical formula is [Ti8Cu5] Cu3, just in time corresponding Ti50Cu50 composition, this also be one through the GFA of experiment confirm Ti-Cu two metamembers preferably.Based on this [Cu-Cu4Ti8] Cu3+[Cu-Cu4Ti8] Cu3 binary " two clusters+connection atom " empirical formula, with [Cu-Cu4Ti8] Cu1+[Cu-Cu4Ti8] the Cu1 situation is similar, utilize similar element substitution method, we can obtain relatively low (～40at.%) the Ti base Ti of Ti content
40.6Zr
9.4Cu
31.3-46.9Ni
15.6-0Sn
3.1Block metal glass composition series.
Adopt high purity constituent element element, by the alloying constituent of above-mentioned design prepare burden; Utilize the non-consumable arc-melting furnace that institute's gold conjugate is carried out repeatedly melting, to obtain the uniform alloy pig of composition; Adopt copper mold casting method then, prepare different diameter (2～10mm) alloy bar, the composition range and the thermodynamic behaviour of analysis and affirmation block metal glass.
Effect of the present invention and benefit are: 1. in the system that does not contain poisonous element Be and precious metals pd, prepared the Ti base metal glass of big formation ability, critical size can reach 7mm; 2. overcome in the complex alloys system arbitrariness problem of choosing of composition proportion between constituent element, according to " two clusters+connection atom " but model quantitative design alloying constituent and then is determined the formation scope of block metal glass; 3. consider that the Ni element has certain side effect to human body.The present invention develops the Ti-Zr-Cu-Sn metallic glass alloys new system that not contain Ni, has good biomedical applications prospect.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Below provide the method for preparing Ti Quito constituent element block metal glass, comprise composition proportion weighing, melting and blow casting, processing step is:
Step 1: design mix with get the raw materials ready
According to the atomic percent in the design mix, convert weight percent (wt.%) to, take by weighing each constituent element weight of alloy, stand-by, high purity metal raw material: Ti is 99.99%, and Zr is 99.99%, and Cu is 99.99%, and Ni is 99.99%, Sn is 99.99%.
Step 2: the melting of alloy pig
To be placed on by the compound of composition proportion weighing in the water jacketed copper crucible of arc-melting furnace, and adopt the non-consumable arc melting method to carry out melting under the protection of argon gas, so melt back is 3 times, obtains the uniform alloy pig of composition;
Step 3: block metal glass preparation
Alloy pig is put into water jacketed copper crucible, adopt the non-consumable arc melting method under the protection of argon gas, to melt, utilize suction casting method to prepare the bar-shaped sample of different size afterwards.
Below provide the technique means that the present invention tests detection.
At first utilize X-ray diffractometer (Bruker D8) that the different diameter alloy bar that makes is carried out structure detection, if show typical non-crystalline state feature on the diffracting spectrum disperse the steamed bun peak, show that then alloy is for being block metal glass; If occurred sharp-pointed bright and sharp diffraction peak on the diffracting spectrum, then show to have generated the crystal phase in the alloy.Whether the different diameter metal bar that can determine the enough copper mold casting formation of energy according to XRD result is metallic glass.
Utilize differential scanning calorimeter (TA Q100) and differential thermal analyzer (TA Q600) to measure the thermodynamical coordinate of block metal glass then, these parameters can be used for characterizing metal stability, glass and formation ability, wherein glass transformation temperature T
gWith crystallization temperature T
xBe the characteristic parameter of characterizing metal glass heat stability, its value increases its value increase and shows the anti-crystallization ability reinforcement of amorphous, and the thermostability of amorphous uprises; T
Rg(=T
g/ T
l) be the important parameter that characterizes alloy GFA, it is worth high, shows that the glass forming ability of alloy is strong.
Subordinate list is the experimental result of typical Ti bast block metal glass among the present invention.T
gSecond-order transition temperature, T
xBe initial crystallization temperature, T
gAnd T
xAll under the heating rate of 40K/min, record; T
mAnd T
lBe respectively the fusing beginning and the finishing temperature of alloy, under the 20K/min heating rate, record.The Ti bast block metal glass new alloy of the present invention's exploitation all has higher T
Rg(＞0.56) shows that these alloys all have good GFA, this with table in the actual glass of the alloy listed to form critical size consistent.
Subordinate list: the experimental result of Ti Quito constituent element system typical case block metal glass
Alloying constituent critical size T
g/ K T
l/ K T
m/ K T
l/ K T
Rg=T
g/ T
l
Ti
50Zr
7.1Cu
28,6Ni
10.7Sn
3.6 3mm 686 710 1150 1221 0.562
Ti
50Zr
7.1Cu
25Ni
14.3Sn
3.6 3mm 688 712 1150 1234 0.558
Ti
46.4Zr
10.6Cu
28,6Ni
10.7Sn
3.6 4mm 683 706 1118 1209 0.565
Ti
40.6Zr
9.4Cu
37.5Ni
9.4Sn
3.1 7mm 703 737 1091 1223 0.575
Ti
40.6Zr
9.4Cu
40.6Ni
6.3Sn
3.1 6mm 698 727 1053 1213 0.576
Ti
40.6Zr
9.4Cu
43.7Ni
3.2Sn
3.1 6mm 694 724 1044 1211 0.573
Ti
40.6Zr
9.4Cu
46.9Sn
3.1 4mm 630 717 1081 1229 0.561
Below in conjunction with the given composition of subordinate list, describe the embodiment of typical Ti bast block metal glass among the present invention in detail.Now with Ti
50Zr
7.1Cu
28,6Ni
10.7Sn
3.6, Ti
40.6Zr
9.4Cu
37.5Ni
9.4Sn
3.1And Ti
40.6Zr
9.4Cu
46.9Sn
3.1Be example, the preparation process of this system block metal glass is described, and the thermodynamics characteristics of this system block metal glass are described in conjunction with subordinate list.
Embodiment 1Ti
50Zr
7.1Cu
28,6Ni
10.7Sn
3.6Block metal glass preparation and performance test thereof
Step 1: the weighing of determining to reach composition proportion of composition
From [Cu-Cu4Ti8] Cu1+[Cu-Cu4Ti8] Cu1 basis cluster empirical formula design mix
Be 4g according to the alloy total mass then, standby by the pure metal constituent element of the various purity of proportioning weighing;
Step 2: the melting of alloy pig
The good compound of weighing is placed in the water jacketed copper crucible of arc-melting furnace, adopts the non-consumable arc melting method to carry out melting under the protection of argon gas, so melt back is 3 times, obtains the uniform alloy pig of composition;
Step 3: the preparation of different size cast alloy rod
Utilize copper mold casting alloy pig to be inhaled the bar-shaped sample of casting 2～10mm;
Step 4: the critical size of block metal glass is determined and performance test
With X-ray diffractometer (Cu K
αRadiation, λ=0.15406nm) analyze alloy bar, the result shows that the critical diameter that the glass of this alloy forms is 3mm.3mm copper mold casting rod has typical amorphous structure feature; Measure the thermodynamical coordinate of this block metal glass with differential scanning calorimeter and differential thermal analyzer, be respectively T
g=686K, T
x=710K, T
m=1150K, T
l=1221K;
Embodiment 2Ti
40.6Zr
9.4Cu
37.5Ni
9.4Sn
3.1Block metal glass preparation and performance test thereof
Step 1: the weighing of determining to reach composition proportion of composition
From [Cu-Cu4Ti8] Cu3+[Cu-Cu4Ti8] Cu3 basis cluster empirical formula design mix
Approximate element substitution alloying obtains [Cu-Cu4Ti6Zr2] Cu2Sn-[Cu-Cu4Ti7Zr1] Ni3
Be 4g according to the alloy total mass then, standby by the pure metal constituent element of the various purity of proportioning weighing;
Step 2: alloy pig melting
Step 3: the preparation of different size cast alloy rod
Step 2 and step 3 are with step 2 among the embodiment one and step 3;
Step 4: the critical size of block metal glass is determined and performance test
X ray detection and hot analytical test are with embodiment one, and the result shows that the critical diameter that the glass of this alloy forms is 7mm; The thermodynamical coordinate that this block metal glass records is respectively T
g=703K, T
x=737K, T
m=1091K, T
l=1223K;
Embodiment 3Ti
40.6Zr
9.4Cu
46.9Sn
3.1Block metal glass preparation and performance test thereof
Step 1: the weighing of determining to reach composition proportion of composition
From [Cu-Cu4Ti8] Cu3+[Cu-Cu4Ti8] Cu3 basis cluster empirical formula design mix
Approximate element substitution alloying obtains
[Cu-Cu4Ti6Zr2]Cu2Sn-[Cu-Cu4Ti7Zr1]Cu3
Be 4g according to the alloy total mass then, standby by the pure metal constituent element of the various purity of proportioning weighing;
Step 2: alloy pig melting
Step 3: the preparation of different size cast alloy rod
Step 2 and step 3 are with step 2 among the embodiment one and step 3;
Step 4: the critical size of block metal glass is determined and performance test
X ray detection and hot analytical test are with embodiment one, and the result shows that the critical diameter that the glass of this alloy forms is 4mm; The thermodynamical coordinate that this block metal glass records is respectively T
g=630K, T
x=717K, T
m=1081K, T
l=1229K.
Claims (1)
1. Ti bast block metal glass, it is characterized in that: do not contain poisonous element Be and expensive precious metals pd, according to " two clusters+connection atom " structural models design titanium base Ti-Zr-Cu (Ni)-the Sn block metal glass, its typical composition scope that forms bulk glass is: Ti
60-50Zr
3.0-7.5Cu
21-32.5Ni
18-7.0Sn
2.0-4.0And Ti
40.6Zr
9.4Cu
31.3-46.9Ni
15.6-0Sn
3.1(atomic percent).
Priority Applications (1)
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|---|---|---|---|
| CN 201010593926 CN102108475B (en) | 2010-12-11 | 2010-12-11 | Ti-based bulk metallic glass |
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|---|---|---|---|
| CN 201010593926 CN102108475B (en) | 2010-12-11 | 2010-12-11 | Ti-based bulk metallic glass |
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Family
ID=44172760
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277543A (en) * | 2011-08-09 | 2011-12-14 | 北京科技大学 | Titanium-based block amorphous alloy with high palladium content and low copper content and preparation method thereof |
| CN104911512A (en) * | 2015-04-17 | 2015-09-16 | 辽宁工业大学 | Method for making bimetallic composite board by using dendrite reinforced titanium-based metal glass composite material and pure titanium |
| CN105132835A (en) * | 2015-09-14 | 2015-12-09 | 西北工业大学 | (Ti-Cu-Ni-Zr)-Sn amorphous composite and preparation method thereof |
| CN105220081A (en) * | 2015-09-30 | 2016-01-06 | 北京航空航天大学 | The insensitive non-crystaline amorphous metal of a kind of impurity |
| CN110614375A (en) * | 2019-09-29 | 2019-12-27 | 西安科技大学 | Preparation method of titanium-based metal glass reinforcement |
| CN114433849A (en) * | 2021-12-06 | 2022-05-06 | 南京工程学院 | Titanium-based metal glass powder rich in double-strong Fenton active elements and preparation method thereof |
| CN116580795A (en) * | 2023-05-16 | 2023-08-11 | 燕山大学 | Component design method of metallic glass based on melting entropy and intermetallic compound |
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| CN1403619A (en) * | 2001-09-13 | 2003-03-19 | 中国科学院金属研究所 | Multicomponent titanium-base alloy to form amorphous structure |
| CN1814850A (en) * | 2006-03-09 | 2006-08-09 | 北京航空航天大学 | Cube titanium non-crystal alloy |
| CN101538694A (en) * | 2008-03-18 | 2009-09-23 | 比亚迪股份有限公司 | Titanium-based amorphous alloy and method for preparing same |
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| CN1403619A (en) * | 2001-09-13 | 2003-03-19 | 中国科学院金属研究所 | Multicomponent titanium-base alloy to form amorphous structure |
| CN1814850A (en) * | 2006-03-09 | 2006-08-09 | 北京航空航天大学 | Cube titanium non-crystal alloy |
| CN101538694A (en) * | 2008-03-18 | 2009-09-23 | 比亚迪股份有限公司 | Titanium-based amorphous alloy and method for preparing same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277543A (en) * | 2011-08-09 | 2011-12-14 | 北京科技大学 | Titanium-based block amorphous alloy with high palladium content and low copper content and preparation method thereof |
| CN102277543B (en) * | 2011-08-09 | 2012-12-05 | 北京科技大学 | Titanium-based block amorphous alloy with high palladium content and low copper content and preparation method thereof |
| CN104911512A (en) * | 2015-04-17 | 2015-09-16 | 辽宁工业大学 | Method for making bimetallic composite board by using dendrite reinforced titanium-based metal glass composite material and pure titanium |
| CN105132835A (en) * | 2015-09-14 | 2015-12-09 | 西北工业大学 | (Ti-Cu-Ni-Zr)-Sn amorphous composite and preparation method thereof |
| CN105220081A (en) * | 2015-09-30 | 2016-01-06 | 北京航空航天大学 | The insensitive non-crystaline amorphous metal of a kind of impurity |
| CN110614375A (en) * | 2019-09-29 | 2019-12-27 | 西安科技大学 | Preparation method of titanium-based metal glass reinforcement |
| CN114433849A (en) * | 2021-12-06 | 2022-05-06 | 南京工程学院 | Titanium-based metal glass powder rich in double-strong Fenton active elements and preparation method thereof |
| CN116580795A (en) * | 2023-05-16 | 2023-08-11 | 燕山大学 | Component design method of metallic glass based on melting entropy and intermetallic compound |
| CN116580795B (en) * | 2023-05-16 | 2023-11-21 | 燕山大学 | Component design method of metallic glass based on melting entropy and intermetallic compound |
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