CN1219905C - Copper base lump non-crystalline alloy - Google Patents
Copper base lump non-crystalline alloy Download PDFInfo
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- CN1219905C CN1219905C CN 02159765 CN02159765A CN1219905C CN 1219905 C CN1219905 C CN 1219905C CN 02159765 CN02159765 CN 02159765 CN 02159765 A CN02159765 A CN 02159765A CN 1219905 C CN1219905 C CN 1219905C
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Abstract
The present invention relates to a copper base bulk amorphous alloy. The copper base amorphous alloy comprises the volume percentage of at least 50% of amorphous phases. The structural formula of the amorphous alloy is Cua-R'b-R'c-Rd, wherein a, b and c are the atomic percentage of corresponding elements; a is more than 45 and less than 66, b is more than 5 and less than 25, c is more than or equal to 5 and at most 20, d is more than or equal to 0 and less than 30, and the sum of a, b, c and d is 100; R' is Zr and/or Hf, and R' is Ti or Nb; R is at least one selected from the elements of Fe, Ni, Y, Be, Al, Sn, Si, etc. The copper base bulk amorphous alloy has the advantages of large dimension, high hardness, good thermal stability, good amorphous formation ability and low requirement to the raw material purity of required each component element, and the copper base bulk amorphous alloy is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of amorphous alloy material, be meant a kind of copper base large amorphous alloy especially.
Background technology
Non-crystaline amorphous metal normally is cooled to the molten metal alloy to solidify formation below the glass transformation temperature and before forming core and crystallization.Common metal and alloy all want crystallization to form crystal when liquid cooled is got off.Yet, having had been found that some metal and alloy when rate of cooling is enough fast, the structure in the time of can keeping liquid state when solidifying suppresses crystallization, and this rate of cooling need reach 10 usually
4～10
6The order of magnitude of K/s.In order to obtain so high rate of cooling, molten metal or alloy can only be sprayed onto on the extraordinary conductive substrate of heat conduction, form non-crystaline amorphous metal like this, but size is very little.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 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 non-crystaline amorphous metal.
Duwez as far back as nineteen sixty just adopt copper roller quick quenching technique prepared AuSi be amorphous ribbon (document 1, W.Klement, R.H.Wilens, 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 can only be low-dimensional materials dimensionally, as strip, filament, fine powder.Mechanical alloying also once was a 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 density with the block metal glass of this method preparation is relatively poor, and sneaks into other impurity easily.So obtaining bulk amorphous alloys is the target that scientists is pursued in decades 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 by the copper mold casting, this is to find that first the millimeter level non-crystaline amorphous metal that does not contain precious metal forms system.The U.S. and Japan have succeeded in developing zirconium-base amorphous alloy in succession since 1993, as Zr
41Ti
14Cu
12Ni
10Be
23, Zr
65Al
7.5Ni
10Cul
7.5Deng, and copper base large amorphous alloy (document 4, A.Peker and W.L.Johnson, Appl.Phys.Lett., 1993, Vol.63, PP2342-44 and document 5, A.Inoue, W.Zhang, T.Zhang and K.Kurosaka, Actamater.2001, vol.49, pp2645-2652).Zirconium-base amorphous being used in very soon on golf club panel, other precision optical instrument parts, corrosion-resistant vessel, bullet or the armour piercing shot bullet core.
In addition, discover that bulk amorphous alloys has the superplastic deformation ability in supercooling liquid phase region, therefore moulding and the processing for alloy provides possibility.
The copper base large amorphous alloy has good mechanical property, and tension, ultimate compression strength are more than 2000Mpa, and elasticity is also fine.The state of the art that the preparation of the copper base bulk-metallic glass of American and Japanese discovery at present requires is very high, needs the alloy of ultra-high purity, generally is higher than 99.999% (document 5, 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).And the size of the copper base bulk-metallic glass that the Japanese did is little, and can only make diameter is the bar-shaped cu-based amorphous alloys of 3-4 millimeter.
Usually, the composition of non-crystaline amorphous metal contains transiting group metal elements and beryllium behind a preceding transiting group metal elements or one at least.The ternary alloy that contains beryllium has good amorphous formation ability usually.Yet the quad alloy that contains at least three transiting group metal elements has the critical cooling rate of the lower crystallization avoided, and therefore has better amorphous formation ability.However, the non-crystaline amorphous metal with better glass forming ability but finds in multicomponent 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 interpolation 5% to 10% all is acceptable in addition in non-crystaline amorphous metal, still can form non-crystaline amorphous metal.In addition, non-crystaline amorphous metal allows to contain a spot of impurity, and for example a spot of oxygen may be dissolved in the non-crystaline amorphous metal and significant crystallization can not take place.The subsidiary element that also may contain other, for example germanium, phosphorus, carbon, nitrogen, but the total amount of impurity should be less than 5% (atomic percent).
Curve a among Fig. 1 and curve b are the crystallization curve of known two kinds of non-crystaline amorphous metals; Fusing point T is understood in the figure acceptance of the bid
mWith glass transformation temperature T
g, the front end of curve has been represented and has been separated out the given required shortest time of crystal volume fraction.In order to obtain a kind of unordered solid material, alloy must be from cooling down by glass transition more than the fusing point and crystallization not taking place, promptly alloy when fusing point cools down by glass transformation temperature can not with the crystallization curve intersection.Crystallization curve a has represented the crystallization behavior of the non-crystaline amorphous metal that very early time obtains, and its rate of cooling has surpassed 10
5K/s is usually 10
6The order of magnitude of K/s.Crystallization curve b is the crystallization curve of the non-crystaline amorphous metal developed afterwards, forms the needed rate of cooling of non-crystaline amorphous metal and has reduced by 1 or 2 even 3 order of magnitude, about 10
3K/s.
Can form non-crystaline amorphous metal and only be the first step that obtains bulk amorphous alloys, what people wanted to obtain is non-crystaline amorphous metal and the machinable parts thereof with big three-dimensional dimension.Make block amorphous alloy can carry out processing treatment and keep its integrity, it is deformable just requiring alloy.Non-crystaline amorphous metal only can be near the glass transformation temperature or abovely could experience uniform deformation under added pressure.In addition, crystallization also takes place in this temperature range usually fast.Therefore as shown in Figure 1, each non-crystaline amorphous metal that forms is reheated glass transformation temperature when above, and there is a very narrow humidity province that crystallization does not take place in non-crystaline amorphous metal before crystallization.
Fig. 2 is known non-crystaline amorphous metal logarithmic relationship figure as the temperature and the viscosity of supercooled liquid between fusing point and glass transformation temperature.At glass transformation temperature, the viscosity of alloy is 10
12The pool order of magnitude.In addition, the viscosity of liquid alloy may be less than 1 pool (the about centipoise(unit of dynamic viscosity of the viscosity of water under the room temperature).Can see that by Fig. 2 the viscosity of non-crystaline amorphous metal reduces with the increase of temperature gradually at cold zone when the heating non-crystaline amorphous metal, changes fast then more than glass transformation temperature.5 degrees centigrade of the every increases of temperature, viscosity reduces an order of magnitude.People wish the viscosity of non-crystaline amorphous metal is reduced to 10
5Pool, so that can make its distortion under less power, this just means and amorphous sample is heated to more than the glass transformation temperature.To processing treatment time of non-crystaline amorphous metal should be on several seconds or the longer time order of magnitude so that have the competent time before appreciable crystallization takes place, heat, operation, processing and cooled alloy.Therefore, for the non-crystaline amorphous metal with good formation ability, people expect that the crystallization curve promptly moves to the longer time to the right.
The ability of non-crystaline amorphous metal opposing crystallization and alloy are relevant from the melt desired rate of cooling of formation amorphous that cools down.This is a unordered mutually stable sign during more than the glass transformation temperature non-crystaline amorphous metal being processed.We expect to suppress the crystalline rate of cooling is from per second 10
3K is to per second 1K or lower.When critical cooling rate reduces, before taking place, crystallization can obtain the longer processing treatment time, and promptly such non-crystaline amorphous metal can fully be heated to more than the glass transformation temperature and process under the situation that crystallization does not take place, and makes it be suitable for industrial use.
Therefore, have lower rate of cooling, better amorphous formation ability, amorphous alloy material large-sized, that intensity is high will be more suitable in industrial use.
Summary of the invention
The objective of the invention is in order to obtain more to be applicable to the amorphous alloy material of industrial use, thereby a kind of copper base large amorphous alloy is provided.
Purpose of the present invention can realize by following measure:
A kind of copper base large amorphous alloy comprises volume percent and is at least 50% amorphous phase in this non-crystaline amorphous metal, the structural formula of this non-crystaline amorphous metal is: Cu
a-R '
b-R "
c-R
d, wherein a, b, c, d are the atomic percent of respective element, 45＜a＜66,5＜b≤30,5≤c≤20,0≤d＜30, and a+b+c+d=100, R ' is Zr and/or Hf, R " be Ti or Nb, R is selected from least a in Fe, Ni, Y, Be, Al, Sn, the Si element.
The arbitrary transiting group metal elements that also contains atomic percent 5%-10% in the described non-crystaline amorphous metal.
Also contain the atomic percent total amount in the described non-crystaline amorphous metal and be less than 5% impurity.
Described impurity comprises at least a in oxygen, germanium, phosphorus, carbon, the nitrogen element.
The material purity of each component of described non-crystaline amorphous metal is 99%-99.999%.
The present invention has following advantage compared to existing technology:
The size of copper base large amorphous alloy provided by the invention is big, the intensity height, and Heat stability is good, amorphous formation ability is good, and the material purity of each required constituent element element requires low, is more suitable for industrial use.
Description of drawings
Fig. 1 is the crystallization curve of known two kinds of non-crystaline amorphous metals and non-crystaline amorphous metal of the present invention;
Fig. 2 is the logarithmic relationship figure of the temperature and the viscosity of known non-crystaline amorphous metal supercooled liquid between fusing point and glass transformation temperature;
Fig. 3 is the X-ray diffractogram of the non-crystaline amorphous metal of embodiments of the invention 1;
Fig. 4 is the X-ray diffractogram of the non-crystaline amorphous metal of embodiments of the invention 2-6;
Fig. 5 is the X-ray diffractogram of the non-crystaline amorphous metal of embodiments of the invention 7 and 8;
Fig. 6 is the differential thermal analysis curve of the non-crystaline amorphous metal of embodiments of the invention 3,4 and 5;
The drawing explanation:
The crystallization curve of the non-crystaline amorphous metal that the a-very early time obtains;
The crystallization curve of the non-crystaline amorphous metal of b-later development;
The crystallization curve of c-non-crystaline amorphous metal of the present invention;
1-non-crystaline amorphous metal Cu
58.8Zr
29.4Ti
9.8Y
22-non-crystaline amorphous metal Cu
60Zr
25Hf
5Ti
10
3-non-crystaline amorphous metal Cu
60Zr
20Hf
10Ti
104-non-crystaline amorphous metal Cu
60Zr
15Hf
15Ti
10
5-non-crystaline amorphous metal Cu
60Zr
10Hf
20Ti
106-non-crystaline amorphous metal Cu
60Zr
5Hf
25Ti
10
7-non-crystaline amorphous metal Cu
60Zr
30Ti
108-non-crystaline amorphous metal Cu
47Ti
34Zr
11Ni
8
Embodiment
The present invention can adopt the electrolytic copper of domestic production, uses the preparation method of known non-crystaline amorphous metal to obtain cu-based amorphous alloys material of the present invention.
Curve c among Fig. 1 is the crystallization curve of non-crystaline amorphous metal of the present invention, and required rate of cooling further greatly reduces, and rate of cooling is no more than per second 10
2K.With 1～100K/s or lower rate of cooling cooling, the scantling that can prepare is not less than 1 millimeter in each dimension with uniform alloy melt.Such rate of cooling can realize by the prior art of multiple non-crystaline amorphous metal preparation: as can adopting teeming practice, the cold copper mold of alloy casting water inlet is obtained being of a size of 1～8 millimeter or bigger tabular, bar-shaped, strip or mesh members; Can adopt water quenching, in quartz container, carry out cold quenching, obtain 8 millimeters or larger sized bar-shaped sample; Also can adopt vacuum suction casting technique, alloy is sucked copper mold, obtain large-sized sample.
The ratio of amorphous phase in non-crystaline amorphous metal can be analyzed and estimate by differential thermal analysis or with transmission electron microscope TEM.
Amorphous phase in the non-crystaline amorphous metal can verify by many known methods.The X-ray diffractogram of non-crystaline amorphous metal is shown as the scattering peak of a wide disperse fully.Fig. 3 to Fig. 5 is the X-ray diffraction analysis figure of non-crystaline amorphous metal of the present invention, as seen from the figure, does not observe any crystallization peak in the effective resolution of X-ray diffractometer, illustrates that prepared alloy is a non-crystaline amorphous metal.In non-crystaline amorphous metal, contain the crystallization phase time, will observe the Bragg diffraction peak of sharp-pointed relatively representative crystallization phase.
Table 1
| Embodiment | Glass transformation temperature T g(K) | Crystallization temperature T X(K) | Fusing point T m(K) | The width Delta T of supercooling liquid phase region (K) | Yield strength (Mpa) | Tensile strength (Mpa) |
| 1 | 714 | 763 | 1057 | 49 | 2030 | 2100 |
| 3 | 712 | 763 | 1067 | 51 | - | 2190 |
| 7 | 706 | 751 | 1175 | 45 | 2010 | 2160 |
| 8 | 705 | 742 | 1058 | 37 | - | 2000 |
| 9 | 712 | 760 | 1085 | 38 | - | 2450 |
| 10 | 708 | 753 | 1081 | 45 | - | 1920 |
| 11 | 718 | 766 | 1140 | 48 | - | 2050 |
Table 1 is the performance of cu-based amorphous alloys of the present invention.The diameter of these alloys is greater than 1 millimeter and be complete amorphous phase.By differential thermal analysis DSC, obtain the performance of non-crystaline amorphous metal, comprise the glass transformation temperature T that represents with absolute temperature
g, crystallization temperature T
X, fusing point T
m, supercooling liquid phase region width Delta T; And by mechanical test test acquisition corresponding strength.Owing to during sample measurement, in argon atmospher, carry out, and the commercial argon gas that uses comprises some oxygen usually, so after sample heated in measuring process, the surface had some oxidations.When the sample surface was cleaned very much so that homogeneous nucleation rather than heterogeneous nucleation take place, crystallization temperature can be higher.Therefore the crystallization temperature height that obtains than the oxidized back of sample surfaces in these trials of the crystallization temperature of actual sample.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 shows that non-crystaline amorphous metal has lower critical cooling rate, and promptly non-crystaline amorphous metal has the longer treatment time more than glass transformation temperature.
Embodiment 1:
Known water quenching is adopted in the preparation of this embodiment: with purity is that 99.5% Cu, Zr, elements such as Ti, Y are by formula Cu
58.8Zr
29.4Ti
9.8Y
2Required atom proportioning is arc melting in the argon atmospher of titanium absorption, makes it to mix, and cooling obtains mother alloy ingot.Pack into after these ingot castings are pulverized in the quartz glass tube, vacuum is extracted into 10
-3Encapsulate behind the Pa, in stove, be heated to 1050 ℃ and keep making the ingot casting remelting in 10 minutes, shrend then, the Cu of acquisition uniform ingredients
58.8Zr
29.4Ti
9.8Y
2The pole of 5 mm dias of bulk amorphous alloys 1.This non-crystaline amorphous metal contains the atomic percent total amount and is about 1% impurity: oxygen and nitrogen.By the X-ray diffractogram of Fig. 3 as seen, all amorphous phase in this non-crystaline amorphous metal 1, no crystallization phase.By table 1 as seen, the fusing point T of this alloy 1
mBe 1057K, crystallization temperature T
xBe 763K, glass transformation temperature T
gBe 714K.Tensile strength is 2100Mpa.
Embodiment 2-6:
Known teeming practice is adopted in the preparation of this serial embodiment.Be that example explanation adopts teeming practice to prepare non-crystaline amorphous metal with embodiment 3 below: with purity is that 99.9% Cu, Zr, Hf, Ti are by Cu
60Zr
20Hf
10Ti
10The proportioning of chemical formula is arc melting in the argon atmospher of titanium absorption, makes it to mix, and 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 10 then
-1Pa, the fusing back is blown in the water cooled copper mould with argon gas, promptly obtains Cu
60Zr
20Hf
10Ti
10Bulk amorphous alloys 3.The X-ray diffractogram of this non-crystaline amorphous metal is seen Fig. 4, and this figure shows in the non-crystaline amorphous metal 3 all be amorphous phase, no crystallization phase.Go back atom per-cent total amount in this non-crystaline amorphous metal 3 and be about 2% germanium, phosphorus and carbon.This alloy 3 is at Cu
60Zr
30Ti
10In the alloy, obtain with metallic element hafnium instead of part Zr.The adding of a spot of metallic element hafnium has improved the amorphous formation ability of alloy, makes alloy have higher and better manufacturability.The differential thermal analysis curve of this non-crystaline amorphous metal 3 is seen Fig. 6.By table 1 as seen, the glass transformation temperature of this non-crystaline amorphous metal 3 is 712K, and its supercooling liquid phase region width is 51K, illustrates that its thermostability and amorphous formation ability are better than the bulk amorphous alloys of embodiment 1 preparation.In addition, adopt teeming practice also to prepare Cu as embodiment 3
60Zr
25Hf
5Ti
10Copper base large amorphous alloy 2; Cu
60Zr
15Hf
15Ti
10Copper base large amorphous alloy 4; Cu
60Zr
10Hf
20Ti
10Copper base large amorphous alloy 5; Cu
60Zr
5Hf
25Ti
10Copper base large amorphous alloy 6; As seen from Figure 4, in the non-crystaline amorphous metal 4 and 5 no crystallization mutually, non-crystaline amorphous metal 4 and 5 differential thermal curve are seen Fig. 6; There is a spot of crystallization to exist mutually in the non-crystaline amorphous metal 2 and 6.
Embodiment 7:
Present embodiment adopts known vacuum suction casting technique: with purity is that 99% Cu, Zr, Ti are by Cu
60Zr
30Ti
10The atom proportioning of chemical formula is arc melting in the argon atmospher of titanium absorption, makes it to mix, and this electric arc furnace has absorbing and casting device, then alloy is sucked copper mold, can obtain glass transformation temperature T
g, initial crystallization temperature T
xBy table 1 as seen, the characteristics of this non-crystaline amorphous metal 7 are to have high fusing point T
m1175K and crystallization temperature T
x751K, so thermostability is fine, the temperature that is suitable for is very high.The glass transformation temperature of this non-crystaline amorphous metal 7 is 706K, and the supercooling liquid phase region width of this alloy is 45K, illustrates that its amorphous formation ability is fine.Tensile strength is 2160Mpa.
Embodiment 8:
With purity is that 99.99% Cu, Zr, Ti, Ni are by Cu
47Ti
34Zr
11N
8The proportioning of chemical formula, it is Cu that the method for employing embodiment 1 is prepared composition
47Ti
34Zr
11Ni
8Bulk amorphous alloys 8, the content of titanium alloy is the highest, the alloying element content that zirconium and other are expensive is less, cost is lower.Fig. 5 shows also do not have the existence of crystallization phase in this non-crystaline amorphous metal 8.By table 1 as seen, the glass transformation temperature of this non-crystaline amorphous metal 8 is 705K, and crystallization temperature is 742K, and fusing point is 1058K, and the sample maximum diameter can reach 4 millimeters, has higher intensity simultaneously again.
Embodiment 9:
With purity is that 99.999% Cu, Zr, Be, Ti are by Cu
54Zr
27Ti
9Be
10The proportioning of chemical formula, it is Cu that the method for employing embodiment 1 is prepared composition
54Zr
27Ti
9Be
10Bulk amorphous alloys.This alloy is at Cu
60Zr
30Ti
10In the alloy, add that a spot of metallic element beryllium obtains.The adding of a spot of metallic element beryllium has improved the amorphous formation ability of alloy, makes alloy have higher and better manufacturability.The sample diameter of this non-crystaline amorphous metal reaches 5 millimeters, and all is amorphous, and its X-ray diffractogram is similar to Fig. 5.By table 1 as seen, the glass transformation temperature of this non-crystaline amorphous metal 9 is 712K, and its supercooling liquid phase region width is 48K, and this example is to utilize the method that increases little atom to improve the formation ability of amorphous.Can prepare the sample of 8 mm dias in addition, contain the amorphous phase of volume percent more than at least 50%.
Embodiment 10:
It is Cu that the method for employing embodiment 3 is prepared composition
47Ti
31Zr
11Ni
8Sn
3Bulk amorphous alloys.This alloy is at Cu
47Ti
34Zr
11Ni
8In the alloy, replace titanium elements to obtain with a spot of metallic element tin.The adding of a spot of metallic element tin has improved the amorphous formation ability of alloy, makes alloy have higher and better manufacturability.By table 1 as seen, the glass transformation temperature of this non-crystaline amorphous metal is 708K, and its supercooling liquid phase region width compares Cu
47Ti
34Zr
11Ni
8Non-crystaline amorphous metal 8 is wideer, illustrates that its thermostability and amorphous formation ability are better than the bulk amorphous alloys of embodiment 4 preparations.Can prepare the complete amorphous sample of 5 mm dias, its X-ray diffractogram is similar to Fig. 5.Also can prepare volume percent and be more than 50%, the amorphous sample of 8 millimeters of diameters.
Embodiment 11: adopting the method for embodiment 7 to prepare diameter is 3 millimeters non-crystaline amorphous metal Cu
60Hf
25Ti
15, by table 1 as seen, the fusing point T of this non-crystaline amorphous metal
mBe 1140K, crystallization temperature T
xBe 766K, glass transformation temperature is 718K.Tensile strength is 2050Mpa.
Embodiment 12: adopting the method for embodiment 1 to prepare diameter is 3 millimeters non-crystaline amorphous metal Cu
60Zr
15Nb
5Hf
10Ti
10
Embodiment 13: it is the non-crystaline amorphous metal Cu of 1-3 millimeter that the method for employing embodiment 3 has prepared diameter
60Zr
28Ti
10Fe
2, wherein the volumn concentration of amorphous phase is greater than 90%;
Embodiment 14: it is the non-crystaline amorphous metal Cu of 1-3 millimeter that the method for employing embodiment 7 has prepared diameter
60Zr
25Ti
10Al
5, wherein the volumn concentration of amorphous phase is greater than 90%; And
Embodiment 15: adopt embodiment 1 method this to have prepared diameter be the non-crystaline amorphous metal Cu of 1-3 millimeter
47Ti
31Zr
11Ni
8Sn
1Si
2, wherein the volumn concentration of amorphous phase is greater than 90%.
The X-ray diffractogram of embodiment 11-15 all is similar to Fig. 5.
Show that by the foregoing description material of the present invention comprises the amorphous phase of at least 50% volume percent.Non-crystaline amorphous metal provided by the invention has high strength, and its value is most of or surpass 2000GPa, can see that from table 1 crystallization temperature of alloy surpasses 730K, and glass transformation temperature surpasses 700K, and this illustrates that they have better thermostability.Non-crystaline amorphous metal provided by the invention is not having crystalline situation lower critical rate of cooling all at 10～100K/s, and has quite wide supercooling liquid phase region, shows that they all have good amorphous formation ability.With three kinds of preparation methods of the present invention, can both obtain the non-crystalline material of millimeter magnitude, overall dimension can reach 8 millimeters.
Claims (1)
1, a kind of copper base large amorphous alloy comprises volume percent and is at least 50% amorphous phase in this non-crystaline amorphous metal, the structural formula of this non-crystaline amorphous metal is: Cu
a-R '
b-R "
c-R
d, wherein a, b, c, d are the atomic percent of respective element, 54≤a≤60,15≤b≤30,5≤c≤10,2≤d≤10, and a+b+c+d=100, R ' is Zr or/and Hf, R " and be Ti or Nb, R is Y or Be.
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| CN1332056C (en) * | 2005-06-07 | 2007-08-15 | 山东大学 | Copper-base amorphous alloy and its preparing proess |
| CN101886234B (en) * | 2010-07-14 | 2011-08-10 | 北京科技大学 | Bulk amorphous alloys of Zr-Cu-Al-Be series and preparation method thereof |
| CN102268616B (en) * | 2011-06-30 | 2014-04-16 | 凡登（常州）新型金属材料技术有限公司 | Cutting steel wire modified by amorphous alloy |
| CN104004976A (en) * | 2013-02-26 | 2014-08-27 | 中兴通讯股份有限公司 | Zirconium-based amorphous alloy, copper-based amorphous alloy, preparation method of amorphous alloy, electronic product structure made by using amorphous alloy, and processing method of electronic product structure |
| CN106893951B (en) * | 2017-03-08 | 2019-02-01 | 黑龙江科技大学 | Cu base bulk metallic glass composite material and preparation method |
| CN109023159B (en) * | 2017-06-08 | 2020-02-21 | 比亚迪股份有限公司 | Copper-based amorphous alloy, preparation method thereof and mobile phone |
| EP3444370B1 (en) | 2017-08-18 | 2022-03-09 | Heraeus Deutschland GmbH & Co. KG | Copper based alloy for the production of metallic solid glasses |
| CN111593272B (en) * | 2020-06-03 | 2021-10-01 | 河海大学 | Corrosion-resistant antifouling copper-based amorphous/carbon nanotube composite material and preparation method thereof |
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