CN1417369A - Low-density blocky metal glass - Google Patents
Low-density blocky metal glass Download PDFInfo
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- CN1417369A CN1417369A CN 01134736 CN01134736A CN1417369A CN 1417369 A CN1417369 A CN 1417369A CN 01134736 CN01134736 CN 01134736 CN 01134736 A CN01134736 A CN 01134736A CN 1417369 A CN1417369 A CN 1417369A
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- 239000011521 glass Substances 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title abstract description 14
- 239000012535 impurity Substances 0.000 claims description 4
- 239000005300 metallic glass Substances 0.000 abstract description 67
- 238000001816 cooling Methods 0.000 abstract description 23
- 239000012071 phase Substances 0.000 abstract description 15
- 239000007791 liquid phase Substances 0.000 abstract description 10
- 238000004781 supercooling Methods 0.000 abstract description 10
- 238000007496 glass forming Methods 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 description 42
- 230000008025 crystallization Effects 0.000 description 42
- 239000000956 alloy Substances 0.000 description 39
- 229910045601 alloy Inorganic materials 0.000 description 37
- 239000010949 copper Substances 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000010936 titanium Substances 0.000 description 23
- 230000009466 transformation Effects 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000010955 niobium Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000013526 supercooled liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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Abstract
The invention relates to low-density blocky metal glass. The series of blocky metal glasses provided by the invention can be represented by the following formula: zra－[Nbx(Ti)1－x]b－(CuyNi1－y)c－[Al]d. Wherein the variation ranges of a, b, c and d are as follows: a is more than 25 and less than 66, b is more than 1 and less than 15, c is more than or equal to 8 and less than or equal to 20, and d is more than 5 and less than 30; the variation range of x and y is as follows: x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1. The metallic glass needs to contain at least 50% by volume of a glass phase. The metallic glass has the advantages of low cooling rate, large size, low density, high hardness, good thermal stability and wide supercooling liquid phase region, and shows that the glass forming capability is good.
Description
The present invention relates to Condensed Matter Physics and material science, particularly relate to metallic glass or non-crystaline amorphous metal field.
Metallic glass normally is cooled to the molten metal alloy to solidify formation below the glass transformation temperature and before forming core and crystallization.Usually, metal and alloy all want crystallization to form crystal when liquid cooled is got off.Yet, found some metal and alloy when rate of cooling is enough fast, the extreme viscous state in the time of when solidifying, can keeping liquid state, thus suppressing crystallization, this rate of cooling need reach per second 10 usually
4～10
6The K order of magnitude.For obtaining so high rate of cooling, molten metal or alloy can only be sprayed onto on the extraordinary conductive substrate of heat conduction.The alloy of Huo Deing is a non-crystaline amorphous metal like this, but size is very little.Therefore, previously obtd amorphous alloy material all is that molten metal or alloy are ejected into the strip that obtains on the copper roller of high speed rotating, or is cast to the thin slice that obtains in the cold substrate and powder etc.Found non-crystaline amorphous metal (metallic glass) recently, so just can utilize lower rate of cooling to suppress crystallization with stronger inhibition crystallizing power.If under very low rate of cooling, can suppress crystallization, then can make larger sized metallic glass.
It is amorphous ribbon (document 1, W.Klement, R.H.Wilens that Duwez just adopts copper roller quick quenching technique to prepare AuSi as far back as nineteen sixty, and Duwez, Nature, 1960, vol.187, pp869-70), contain subsequently metalloid element (as Si, C, B, Ge, non-crystaline amorphous metal P), particularly ferrous alloy are by big quantity research.But because the amorphous formation ability of most of alloy is very poor, if need be higher than 10 with fast cold preparation
6The rate of cooling of K/s is so the non-crystaline amorphous metal that makes (metallic glass) can only be low-dimensional materials dimensionally, as strip, filament, fine powder.Mechanical alloying also once was a kind of method of preparation amorphous powder, and many alloys can change amorphous into by high-energy ball milling, can press amorphous powder in supercooling liquid phase region subsequently and form amorphous block.Yet the block metal glass density with this method preparation is relatively poor, and easily sneaks into other impurity.This external irradiation also can make amorphous metalization, as ion implantation etc.What deserves to be mentioned is that the alloy of precious metal element Pt and Pd has higher amorphous formation ability (as PtNiP, PdNiP), can pass through B
2O
3Refining repeatedly, obtain diameter 10mm spherical sample (document 2, H.S.Chen, Mater.Sci.Eng., 1976, Vol.23, pp151-54).So obtaining bulk-metallic glass is the target that people pursue always.
Up to 1989, the Inoue of Japan etc. has found that MgCuY and LaAlNi are that alloy has very high amorphous formation ability (document 3, A.Inoue, T.Zhang, and T.Masumoto, Mater.Trans., JIM, 1989, Vol.30, pp965-72), can prepare millimetre-sized non-crystaline amorphous metal (metallic glass) by the copper mold casting, this is a millimeter level non-crystaline amorphous metal system of finding not contain precious metal first.Alloy systems such as ZrAlNi, ZrAlCu and ZrAlNiCu have been found subsequently again.1993, the U.S. and Japan succeeded in developing Zr in succession
41Ti
14Cu
12Ni
10Be
23And Zr
65Al
7.5Ni
10Cu
10Al
7.5Bulk-metallic glass (document 4, A.Peker and W.L.Johnson, Appl.Phys.Lett., 1993, Vol.63 PP2342-44), and is used on golf club panel, other precision optical instrument parts, corrosion-resistant vessel, bullet or the armour piercing shot bullet core very soon.Discover that in addition bulk-metallic glass has the superplastic deformation ability in supercooling liquid phase region, for the moulding of alloy and processing provide may.
But the formation of metallic glass is faced with difficulty, crystallization always when promptly the alloy melt of high undercooling solidifies.Crystallization is finished by forming core and crystal growing process.The supercooled liquid crystallization is generally very fast.Form the non-crystaline amorphous metal solid, must be with the mother alloy liquation from temperature of fusion T
mBe cooled to glass transformation temperature T
gBelow and crystallization does not take place.It is very high that the U.S. and Japanese scientist find that the preparation of zirconium base bulk-metallic glass requires state of the art, needs the zirconium of ultra-high purity, generally needs to purify and ultrahigh vacuum(HHV) (document 5 through the district is molten, C.T.Liu, L.Heatherly, D.S.Easton, C.A.Carmicheal, J.H.Schneibel, C.H.Chen, J.L.Wright, M.H.Yoo, J.A.Horton, and A.Inoue, Metallurgical and Materials Transaction A, 1998, Vol 29A, pp1811-1820).
The objective of the invention is to overcome the deficiency of prior art, utilize the existing pure element of China, alloy material and equipment to obtain a series of bulk-metallic glass, this material can be formulated as: Zr
a-[Nb
x(Ti)
1-x]
b-(Cu
yNi
1-y)
c-[Al]
dWherein the variation range of a, b, c, d is: 45＜a＜66,1＜b＜15,12≤c≤20,5＜d＜30; The variation range of x, y is: 0≤x≤1,0≤y≤1.This material need comprise the glassy phase (amorphous phase) of at least 50% volume percent.Metallic glass of the present invention reduces its density because of the adding of a large amount of aluminium greatly, and critical cooling rate is low (less than 10
3K/s), size big (being not less than 1 millimeter) in each dimension.
The object of the present invention is achieved like this:
Fig. 1 is typical metallic glass heat content and temperature curve, and wherein crystallization curve a is the logarithmic curve of temperature and time, indicates fusing point T among the figure
mWith glass transformation temperature T
g, the front end representative of curve is separated out the given required shortest time of crystal volume fraction.For obtaining unordered solid material, alloy must be from cooling down by glass transition more than the fusing point and crystallization is not taken place, promptly alloy when fusing point cools down by glass transformation temperature can not with the crystallization curve intersection.The crystallization behavior of the metallic glass that this curve a representative obtains in early days, its rate of cooling surpasses 10
5K/s is usually 10
6The K/s order of magnitude.Curve b is the crystallization curve of the metallic glass of back exploitation, forms the required rate of cooling of metallic glass and has reduced by 1,2 even 3 order of magnitude.Curve c is the crystallization curve of metallic glass that the present invention does, and required rate of cooling reduces (per second 2 * 10 more greatly
2About K).
Forming metallic glass only is the first step that obtains bulk-metallic glass, and people wish to obtain having metallic glass and machinable parts of big three-dimensional dimension.For making block metal glass can carry out processing treatment and keeping its integrity, just require its deformable.Metallic glass only can near the glass transformation temperature or above could be in uniform deformation under the pressure.And crystallization also takes place in this temperature range usually fast.As Fig. 1, the metallic glass of formation is reheated glass transformation temperature when above, and only there is a very narrow humidity province that crystallization does not take place in it before crystallization.
Fig. 2 is metallic glass temperature and viscosity logarithm synoptic diagram as supercooled liquid between fusing point and glass transformation temperature.At glass transformation temperature, its viscosity is 10
13The pool order of magnitude.In addition, the viscosity of liquid alloy may be less than 1 pool (about 1% pool of the viscosity of water under the room temperature).As shown in Figure 2, when heating of metal glass, its viscosity increases and reduces gradually with temperature at cold zone, and changes fast more than glass transformation temperature.5 ℃ of the every increases of temperature, viscosity reduces an order of magnitude.People wish its viscosity is reduced to 10
5Pool so that can make its distortion under less pressure, this means and this sample should be heated to more than the glass transformation temperature.To treatment time of metallic glass should be on several seconds or the longer time order of magnitude, so that operations such as grace time heats before appreciable crystallization takes place, processing, cooling are arranged.So to having the metallic glass of good formation ability, people expect that the crystallization curve promptly moves to the longer time to the right.The ability of metallic glass opposing crystallization is relevant from the melt required rate of cooling of formation amorphous that cools down with it.This promptly more than the glass transformation temperature to unordered mutually stable sign during the metallic glass processing.Expectation suppresses the crystalline rate of cooling from per second 10
3K is to per second 1K or lower.When critical cooling rate reduces, before taking place, crystallization can obtain longer process period, and promptly such metallic glass can fully be heated to and process more than the glass transformation temperature to be suitable for industrial use under the situation that crystallization does not take place.
Metallic glass provided by the invention can be used following formulate: Zr
a-[Nb
x(Ti)
1-x]
b-(Cu
yNi
1-y)
c-[Al]
dWherein the variation range of a, b, c, d is: 45＜a＜66,1＜b＜15,12≤c≤20,5＜d＜30; The variation range of x, y is: 0≤x≤1,0≤y≤1.
At least contain transiting group metal elements and aluminium behind a preceding transiting group metal elements or one in this metallic glass composition.Aluminiferous ternary alloy has good glass forming ability usually.And the quad alloy that contains at least three transiting group metal elements has the critical cooling rate of the lower crystallization avoided, so have better glass forming ability.And the metallic glass with better glass forming ability is found in quinary alloy, particularly after containing at least two preceding transiting group metal elements and at least two in the alloy of transiting group metal elements.
Usually, any transiting group metal elements of 5% to 10% all can be accepted in metallic glass.And allow to contain small amount of impurities, may be dissolved in the metallic glass as a spot of oxygen and remarkable crystallization does not take place.Also can contain other subsidiary element, as germanium, phosphorus, carbon, nitrogen, but total impurities should be less than 5% (atomic percent).
Above-mentioned formula is a kind of in the various expression alloying constituent methods.In equation expression, generally express various element proportions with algebraically, this ratio interdepends.Some accounts for a high proportion of element of glassy phase that keeps can overcome the tendency that other element promotes crystallization.
Some accounts for the performance that can influence metallic glass than the element of small proportion.Can increase its glass forming ability as titanium and niobium, but content should total amount 15% in, most preferably less than 7.5%.In the metallic glass that contains zirconium, niobium, the content of niobium should be less than 8%, otherwise easily forms glass composite material.
Starting material of the present invention need comprise the glassy phase of at least 50% volume percent.
That adopts domestic production decomposes the zirconium rod of purifying through iodide, can prepare a series of zirconium base bulk-metallic glass that are suitable for domestic resources characteristic and are easy to the technology realization.
Can use the method for traditional preparation process metallic glass to obtain metal glass material of the present invention.Get rid of preparation band, paper tinsel and thin slices such as band or two rolling sheets as single roller.Specific implementation is as follows:
With 1～200K/s or more low rate cooling, the scantling of preparing is not less than 1 millimeter in each dimension with uniform alloy melt.This rate of cooling can realize by multiple technologies: as the cold copper mold of alloy casting water inlet being obtained be of a size of 1～10 millimeter or bigger tabular, bar-shaped, strip or mesh members; Electric arc furnace is inhaled casting etc.
1) teeming practice: purity is not less than 99.8% Zr, Nb, Cu, Ni, Al by required atom proportioning arc melting in the argon atmospher of titanium absorption, make it to mix and (be fused in the alloy for making dystectic niobium, can first melting zirconium, niobium), cooling obtains mother alloy ingot.With melting in high frequency furnace after the mother alloy ingot fragmentation, vacuum tightness is not less than 10 in the stove
-1Pa, the fusing back is blown in the water cooled copper mould with argon gas.
2) vacuum suction casting technique: purity is not less than 99.8% Zr, Nb, Cu, Ni, Al by required atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix, this electric arc furnace has absorbing and casting device, and alloy is injected copper mold.
Glassy phase proportion in the gained metallic glass can be estimated by differential thermal analysis: the heat content that discharges when being about to the heating of complete vitrifying sample and partially-crystallized sample compares, and its ratio can provide glassy phase shared molar fraction in raw sample; Also available tem study (TEM) is determined the ratio of glassy phase in metallic glass.The difference that glass material shows in the electronic microscope photos method is very little, and the crystallization material difference is very big, is easy to difference.Available transmission electron diffraction (TED) method is differentiated phase.The also available transmission electron microscopy image of the volume fraction of the glass material in the sample is estimated.
Glassy phase in the gained metallic glass can be checked by many methods.The X-ray diffractogram of complete metal glass shows the scattering peak of a wide disperse.Fig. 3 to Fig. 5 is the X-ray diffraction analysis figure of part metals glass of the present invention listed in the table 1, can find out and not observe the crystallization peak in the X-ray diffractometer effective resolution, illustrates that gained is a metallic glass.If contain the crystallization phase in the metallic glass, can observe the Bragg diffraction peak of sharp-pointed relatively representative crystallization phase.
Table 1 is the bar-shaped metallic glass table of the present invention that obtains with teeming practice and vacuum suction casting technique, at least 1 millimeter of their diameter or bigger, and be complete glassy phase.Its performance comprises the glass transformation temperature (T with degree centigrade expression
g), crystallization temperature (T
x), fusing point (T
m), width (Δ T), hardness (HV) and the density (ρ) of supercooling liquid phase region, its temperature measurement technology is differential thermal analysis (DSC).Crystallization temperature is that the metallic glass sample is heated to more than the glass transformation temperature for 10 ℃ with per minute, enthalpy change indicated temperature when the crystallization of record begins.Because sample measurement is to carry out in argon atmospher, used commercial argon gas contains some oxygen usually, thus sample after adding thermal measurement, the surface has some oxidations.When the sample surface was cleaned so that homogeneous nucleation is taken place very much, crystallization temperature can be higher.The crystallization temperature of historical facts or anecdotes border sample is than the oxidized back of the sample surfaces temperature height that obtains in the test.The supercooling liquid phase region width is the poor of the crystallization temperature that obtains in differential thermal analysis is measured and glass transformation temperature.Usually the supercooling liquid phase region of broad represents that metallic glass has lower critical cooling rate.Be that metallic glass has the more long process time more than glass transformation temperature.
Metallic glass provided by the invention has low density, high rigidity (hardness value most of near or surpass 6Gpa), and high Vicker hardness has indicated high strength.As shown in Table 1, the crystallization temperature of most of metallic glass surpasses 700K, and glass transformation temperature surpasses 650K, and its Heat stability is good is described.The critical cooling rate of metallic glass of the present invention under no crystallization situation is all at 1～200K/s, and supercooling liquid phase region is quite wide, promptly has good glass forming ability.The metallic glass size that is obtained is all in the millimeter magnitude, and maximum can reach 20 millimeters.
The present invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is the heat content of typical metallic glass and the curve of temperature,
Fig. 2 is metallic glass logarithm synoptic diagram as the temperature and the viscosity of supercooled liquid between fusing point and glass transformation temperature,
Fig. 3～Fig. 5 is the X-ray diffractogram of metallic glass of the present invention,
Fig. 6 is heat analysis (DTA) curve of several metallic glasss of the present invention,
Fig. 7 is heat analysis (DSC) curve of several metallic glasss of the present invention.
Embodiment 1:
Purity is not less than 99.8% Zr, Ti, Cu, Ni, Al by required atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix, cooling obtains mother alloy ingot.With melting in high frequency furnace after the mother alloy ingot fragmentation, the vacuum tightness of high frequency furnace vacuum chamber is not less than 10 then
-1Pa, the fusing back is blown in the water cooled copper mould with argon gas.The bulk-metallic glass composition of preparing is Zr
53Ti
5Cu
20Ni
12Al
10Its fusing point T
mBe 1098K, crystallization temperature T
xBe 747.5K, glass transformation temperature is 670.5K, and the supercooling liquid phase region width is 77K, illustrates that thermostability and glass forming ability are all better.This metallic glass density 6.75g/cm
3, hardness 5.36Gpa, Young's modulus is the 92.7Gpa (see figure 3).
Embodiment 2:
Technical scheme such as embodiment 1, the composition of the bulk amorphous alloys of preparing are Zr
49.5Ti
4.7Cu
18.6Ni
11.2Al
16This alloy is at Zr
53Ti
5Cu
20Ni
12Al
10In the alloy, be added to that the relative content of aluminium obtains.The increase of the relative content of aluminium has reduced the content of zirconium and copper, nickel, the cost of the alloy of reduction, and improved the amorphous formation ability of alloy, make alloy have higher and better manufacturability.The characteristics of this alloy are to have higher fusing point T
m(1l18K) with crystallization temperature T
x(793K), its glass transformation temperature is 697K, and its supercooling liquid phase region width is 96K, illustrates that its thermostability and amorphous formation ability are better than the bulk amorphous alloys of embodiment 1 preparation.The density of this alloy is 6.55g/cm
3
Embodiment 3:
Preparation scheme such as embodiment 1, the bulk-metallic glass base of preparing composition multiple and material is Zr
47Ti
4Cu
17.5Ni
11Al
20.5This material is at Zr
53Ti
5Cu
20Ni
12Al
10The middle relative content gained that increases aluminium.Its crystalline state phase is of a size of nano level and forms under the same conditions with glassy phase, has eliminated by crystallization process and has obtained matrix material, the defective that its strength and toughness worsens.
Embodiment 4:
Purity is not less than 99.8% Zr, Ti, Cu, Ni, Al by required atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix the back and suck in the water-cooled copper mold.Prepare the listed bulk ZrTiCuNiAl glass material of table 1, such material has the identical thermodynamic property of embodiment 1,2.This technology has improved the efficient of glass preparation greatly, has reduced cost.
Embodiment 5:
Purity is not less than 99.8% Zr, Nd, Cu, Ni, Al by required atom proportioning arc melting in the argon atmospher of titanium absorption, makes it to mix the back and suck in the water-cooled copper mold, obtain Zr
57Nb
5Cu
16Ni
12Al
10Massive metal glass material.It obtains with Ti in the Nb alternative embodiment 1.Can make the pole of diameter more than 8 millimeters with the copper mold technology.This material can carry out superplastic deformation in 410 ℃ of air, still be glass structure after the distortion, so highly beneficial to the moulding of material.Its fusing point T
mBe 1132K, crystallization temperature T
xBe 751K, glass transformation temperature is 665K.Its supercooling liquid phase region width can reach 86K, illustrates that its thermostability is better than embodiment 1.Its density is 6.77g/cm
3, hardness is 5.32GPa, Young's modulus is 90.7GPa.
Table 1
| Composition | T g，K | T x，K | ?T m，K | ?ΔT，K | ????HV， ????GPa | ????ρ， ???g/cm 3 |
| Zr 57Nb 5Cu 16Ni 12Al 10 | ??665 | ??751 | ??1132 | ??86 | ????5.32 | ????6.77 |
| [Zr 0.589Ti 0.056Cu 0.222Ni 0.133] 88Al 12 | ??672 | ??770 | ??1118 | ??98 | ????6.70 | |
| [Zr 0.589Ti 0.056Cu 0.222Ni 0.133] 85.7Al 14.3 | ??679 | ??781 | ??1118 | ??102 | ????5.92 | ????6.59 |
| [Zr 0.589Ti 0.056Cu 0.222Ni 0.133] 81.8Al 18.2 | ??689 | ??798 | ??1118 | ??98 | ????6.49 | ????6.44 |
| Zr 52.5Ti 2.5Cu 20Ni 10Al 15 | ??638 | ??708 | ??1098 | ??70 | ????5.20 | ????6.49 |
| Zr 50Ti 8Cu 20Ni 12Al 10 | ??663 | ??758 | ??95 | |||
| [Zr 0.589Ti 0.056Cu 0.222Ni 0.133] 84Al 16 | ??683 | ??788 | ??1118 | ??105 | ????6.50 | |
| Zr 55Nb 2Ti 5Cu 16Ni 12Al 10 | ??670 | ??761 | ??91 | |||
| Zr 65Al 7.5Ni 10Cu 17.5 | ??645 | ??719 | ??1102 | ??74 |
Claims (4)
1. low-density blocky metal-glass is characterized in that: use following formulate:
Zr
a-[Nb
x(Ti)
1-x]
b-(Cu
yNi
1-y)
c-[Al]
dWherein the variation range of a, b, c, d is: 25＜a＜66,1＜b＜15,8≤c≤20,5＜d＜30; The variation range of x, y is: 0≤x≤1,0＜y≤1.
2. by the described low-density blocky metal-glass of claim 1, it is characterized in that: any transiting group metal elements that also can contain 5% to 10% atomic percent.
3. by the described low-density blocky metal-glass of claim 1, it is characterized in that: also can contain total amount and be less than 5% atomic percent impurity.
4. by the described low-density blocky metal-glass of claim 1, it is characterized in that: the glassy phase that need comprise at least 50% volume percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011347368A CN1188540C (en) | 2001-11-09 | 2001-11-09 | Low-density blocky metal glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011347368A CN1188540C (en) | 2001-11-09 | 2001-11-09 | Low-density blocky metal glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1417369A true CN1417369A (en) | 2003-05-14 |
| CN1188540C CN1188540C (en) | 2005-02-09 |
Family
ID=4672711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011347368A Expired - Fee Related CN1188540C (en) | 2001-11-09 | 2001-11-09 | Low-density blocky metal glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1188540C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013087040A1 (en) * | 2011-12-15 | 2013-06-20 | Shenzhen Byd Auto R&D Company Limited | Method of manufacturing amorphous alloy article |
| WO2014004152A1 (en) * | 2012-06-25 | 2014-01-03 | Crucible Intellectual Property, Llc | High thermal stability bulk metallic glass in the zr-nb-cu-ni-al system |
| CN104664152A (en) * | 2015-02-06 | 2015-06-03 | 江西省农业科学院畜牧兽医研究所 | Method of extracting polysaccharides and flavonoids from mulberry leaves and application of polysaccharides and flavonoids to feed |
| CN113774294A (en) * | 2020-06-09 | 2021-12-10 | 株式会社Bmg | Zirconium-based metallic glass alloy |
| CN113913710A (en) * | 2021-10-14 | 2022-01-11 | 盘星新型合金材料(常州)有限公司 | Be-free low-density bulk amorphous alloy and preparation method and application thereof |
| CN113930695A (en) * | 2021-10-14 | 2022-01-14 | 盘星新型合金材料(常州)有限公司 | Al-containing low-density block amorphous alloy and preparation method and application thereof |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
-
2001
- 2001-11-09 CN CNB011347368A patent/CN1188540C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013087040A1 (en) * | 2011-12-15 | 2013-06-20 | Shenzhen Byd Auto R&D Company Limited | Method of manufacturing amorphous alloy article |
| WO2014004152A1 (en) * | 2012-06-25 | 2014-01-03 | Crucible Intellectual Property, Llc | High thermal stability bulk metallic glass in the zr-nb-cu-ni-al system |
| US10066276B2 (en) | 2012-06-25 | 2018-09-04 | Crucible Intellectual Property, Llc | High thermal stability bulk metallic glass in the Zr—Nb—Cu—Ni—Al system |
| CN104664152A (en) * | 2015-02-06 | 2015-06-03 | 江西省农业科学院畜牧兽医研究所 | Method of extracting polysaccharides and flavonoids from mulberry leaves and application of polysaccharides and flavonoids to feed |
| CN113774294A (en) * | 2020-06-09 | 2021-12-10 | 株式会社Bmg | Zirconium-based metallic glass alloy |
| CN113913710A (en) * | 2021-10-14 | 2022-01-11 | 盘星新型合金材料(常州)有限公司 | Be-free low-density bulk amorphous alloy and preparation method and application thereof |
| CN113930695A (en) * | 2021-10-14 | 2022-01-14 | 盘星新型合金材料(常州)有限公司 | Al-containing low-density block amorphous alloy and preparation method and application thereof |
| CN113981335A (en) * | 2021-10-29 | 2022-01-28 | 盘星新型合金材料(常州)有限公司 | Trace element modified Be-free block amorphous alloy and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1188540C (en) | 2005-02-09 |
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