CN100368575C - Magnesium alloy cast into amorphous block with centimeter size - Google Patents

Magnesium alloy cast into amorphous block with centimeter size Download PDF

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CN100368575C
CN100368575C CNB2005100461850A CN200510046185A CN100368575C CN 100368575 C CN100368575 C CN 100368575C CN B2005100461850 A CNB2005100461850 A CN B2005100461850A CN 200510046185 A CN200510046185 A CN 200510046185A CN 100368575 C CN100368575 C CN 100368575C
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alloy
amorphous
pole
copper mold
magnesium alloy
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CN1844433A (en
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麻晗
徐坚
史玲玲
郑强
沈勇
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Abstract

The present invention provides magnesium alloy capable of forming centimeter dimension amorphous block body materials, which is characterized in that the expression of the components of the alloy is Mg<a>(Cu<1-x>Ag<x>) bTyRcXz, wherein the a, the b, the c and the z are atomic percentages; the T is selected from at least one of the elements of Ni, Zn and Pd; the R is selected from at least one of the elements of Y, Gd, Nd and Mm; the X is selected from at least one of the elements of Zr, Nb and Cr; a=45% to 65%; (b+y) =25% to 45%; (c+z) =8% to 15%; a+b+y+c+z=100%; x=0.01 to 0.5; y<=5%; z<=2%. The magnesium alloy provided by the present invention can be cast into an amorphous alloy block body material or a part with a critical size of 0.4 to 2.5 centimeters by using a copper mould casting method.

Description

One class can be cast the magnesium alloy that forms centimeter scale amorphous block material
Technical field:
The present invention relates to amorphous alloy (or metallic glass), provide a class can adopt the copper mold casting to form the magnesium alloy of centimeter scale amorphous block material especially
Background technology:
For common polycrystalline metal material, the primary structure of amorphous alloy (also claiming metallic glass) is characterized as atomic arrangement does not have the macrocyclic degree of order, does not have crystal boundary yet.Therefore have excellent performances such as high strength, corrosion-resistant, isotropy.Be with a wide range of applications in fields such as automobile, aircraft, micromachine, microelectronics, sports goods, precision instrument, burglary-resisting installation, energy transformation, medical materials.Crystallization will take place during from liquid cooled in common Metal and Alloy, be frozen into the material of polycrystal structure.Amorphous alloy normally is cooled to alloy melt the glass transformation temperature that is lower than it and (generally uses T gExpression), avoids taking place tangible crystal forming core and crystallization, thereby solidify the metallic substance that forms non-crystalline state (or vitreous state) structure.
From the sixties in 20th century, can produce cold (be lower than melting temperature crystallization does not still take place) if it is found that some alloy when cooling off with enough fast rate of cooling, at room temperature still remain extremely viscid liquid phase or glassy phase.Required typical rate of cooling is approximately 10 4K/ second to 10 6K/ second.In order to realize fast like this rate of cooling, a spot of alloy melt need be contacted with near remaining on room temperature heat-conducting substrate (as copper coin).The reason of restriction amorphous material yardstick mainly is owing to must extract heat to suppress crystallisation process with enough fast speed.Therefore, Fa Zhan most of amorphous alloys were merely able to obtain forms such as powder, strip, filament, thin slice in the past, these powder, strip, filament, thin slice can by on the cooling copper roller that alloy melt is injected in twirl, be dropped between the refrigerative metal hammer anvil or and obtain by narrow methods such as nozzle with refrigerative substrate quick travel.
Opposing crystalline ability shows as the size that the melt cooling forms the required critical cooling rate of non-crystalline state during the alloy melt cooling.For the ease of actual production widely or application, needed desirable rate of cooling takes place in the inhibition crystallization is 10 -1～10 2K/ order of magnitude second or lower.Along with the reduction of the critical cooling rate of alloy own, people can prepare the amorphous component with bigger cross section.Such alloy can have adequate time to carry out plant-scale processing treatment when being heated to supercooled liquid, and crystallization does not take place.Critical cooling rate roughly with square being inversely proportional to of block materials geometrical dimension, that is: R c = 10 t 2 . R wherein cExpression critical cooling rate (unit is K/ second), t are represented thickness (centimetre to be unit).R cMore little, t is big more.In recent years, people can cast the bulk amorphous alloy that forms centimetre magnitude thickness or diameter at zirconium base, palladium base, platinum base, yttrium base, calcium base, iron-based, copper base, lanthanum base, neodymium base etc. with copper mold for having found in the alloy of principal element in succession.The glass of these alloys form critical speed on the order of magnitude less than 10K/ second.
Usually, the intrinsic amorphous formation ability of alloy and the thermostability of alloy melt mainly depend on the chemical ingredients of alloy, and very responsive to the variation of composition.In some cases, the variation of constituent content 1% (atomic percent) can cause the variation significantly of amorphous formation ability.Complicated or the diversification of alloying constituent (promptly being made up of multiple alloying element) can improve the intrinsic glass forming ability that improves alloy, reduces the critical cooling rate that glass forms.For magnesium alloy, have now found that Mg-Zn binary alloys such as (Ga, Gd), Mg-Zn (Sn)-Ga, Mg-Zn-Au, Mg-Cu-Ca, Mg-TM-X (TM is Cu or Ni), X is Sn, Si, Ge, Zn, Sb, Bi or In), (TM is Cu or Ni to Mg-TM-RE, RE is Rare Earth Y, Gd, Nd, La, Ce or Te), (TM is Cu or Ni to Mg-TM-AE, AE is alkaline earth Ca, Sr or Ba) etc. ternary alloy, Mg-Cu-Zn (Al, Ag, Li)-quad alloys such as Y can be by melt cooling formation amorphous alloy at some specific composition range.It is widely different that different-alloy forms amorphous critical cooling rate, and scope is from 10 6K/ order of magnitude second is to 50K/ order of magnitude second.The glass of the above alloy of ternary forms critical cooling rate and is starkly lower than binary alloy, has stronger amorphous formation ability.For example, Mg 65Cu 20Zn 5Y 10It is the metallic glass pole of 6mm that (being designated as atomic percent down) alloy can adopt copper Mo casting to form diameter.
The density of magnesium only is 1.738 gram/cubic centimetres.Magnesium alloy is a structural metallic materials the lightest in the practical application.Compare with engineering plastics with other common structural metallic materials, magnesium alloy has a lot of excellent characteristic: low as density, specific tenacity is high, machining property is good, castibility and damping shock absorption is good, thermal conductivity is high, dimensional stability is high, capability of electromagnetic shielding is good, attractive in appearance, be easy to recycle etc.The content of magnesium in the earth's crust is quite abundant, and has the very high rate of recovery.Therefore magnesium alloy also is described as " the green engineering material of 21 century ".In view of these characteristics, the magnesium alloy demand that in industries such as automobile, communication, electronics, electrical equipment, Aeronautics and Astronautics, traffic, metallurgy, chemistry, electrochemistry, all is widely used.
The amorphous magnesium alloy has very high intensity, its yield strength is about 600～800 MPas, be 2 to 4 times of common polycrystal cast magnesium alloys, almost can compare favourably with ferrous materials, but density is 3～4 gram/cubic centimetres, therefore has very high specific tenacity, can have tangible weight loss effect as structured material, magnesium alloy with strong amorphous formation ability can be used for preparing bar, the sheet material of bigger geometrical dimension or directly is cast as component, satisfies application demand more widely.
Summary of the invention:
The present invention will provide the magnesium alloy that a class is easy to prepare becomes amorphous structure, can form the amorphous block material or the component of centimeter scale with the method for common copper mold casting.This class material has the characteristics of high strength, low density, high specific strength.
The invention provides a class and can adopt the copper mold casting to form the multicomponent magnesium alloy of amorphous structure, the expression formula of its alloying constituent is: Mg a(Cu 1-xAg x) bR cA wherein, b, c are atomic percent, R is at least a among element Y, Gd, Nd, the Mm, a=45～65%, b=25～45%, c=8～15%, a+b+c=100%, x=0.01～0.5.After the alloy melt of this composition range is poured into the copper mold inner chamber, can form the block materials or the component of amorphous structure.
The invention provides a class and can adopt the copper mold casting to form the multicomponent magnesium alloy of amorphous structure, the expression formula of its alloying constituent is: Mg a(Cu 1-xAg x) bT yR cA wherein, b, c, y are atomic percent, and T is at least a among element Ni, the Pd, and R is at least a among element Y, Gd, Nd, the Mm, a=45～65%, (b+y)=25～45%, c=8～15%, a+b+y+c=100%, x=0.01～0.5, y≤5%.After the alloy melt of this composition range is poured into the copper mold inner chamber, can form the block materials or the component of amorphous structure.
The invention provides a class and can adopt the copper mold casting to form the multicomponent magnesium alloy of amorphous structure, the expression formula of its alloying constituent is: Mg a(Cu 1-xAg x) bR cX z, a wherein, b, c, z are atomic percent, R is at least a among element Y, Gd, Nd, the Mm, and X is at least a among element Zr, Nb, the Cr, a=45～65%, b=25～45%, (c+z)=8～15%, a+b+c+z=100%, x=0.01～0.5, z≤2%.After the alloy melt of this composition range is poured into the copper mold inner chamber, can form the block materials or the component of amorphous structure.
The invention provides a class and can adopt the copper mold casting to form the multicomponent magnesium alloy of amorphous structure, the expression formula of its alloying constituent is: Mg a(Cu 1-xAg x) bT yR cX z, a wherein, b, y, c, z are atomic percent, T is at least a among element Ni, the Pd, and R is at least a among element Y, Gd, Nd, the Mm, and X is at least a among element Zr, Nb, the Cr, a=45～65%, (b+y)=25～45%, (c+z)=8～15%, a+b+y+c+z=100%, x=0.01～0.5, y≤5%, z≤2%.After the alloy melt of this composition range is poured into the copper mold inner chamber, can form the block materials or the component of amorphous structure.
In the multicomponent amorphous magnesium alloy of the present invention, oxygen level preferably is no more than 0.1% (weight percent).
Multicomponent magnesium alloy provided by the invention has good amorphous formation ability, through the block materials of melt copper mold casting can formation amorphous structure.The geometrical shape of foundry goods depends on the melt employed copper mold inner chamber design of casting, can be the component of shapes such as right cylinder, prism, thin plate, polyhedron, the copper mold quality is not less than 15 kilograms, to guarantee the having heat that enough big thermal capacitance absorbs melt, reduce the copper mold temperature rise that the melt cooling of casting back causes.The temperature rise of mould should be lower than 5 ℃.Under the mould condition of using cylindrical cavity, the critical thickness (or diameter) that alloy forms complete amorphous structure block is 0.4～2.5 centimetre.The alloy of heterogeneity forms the critical size difference of amorphous block material.Under the prerequisite that all forms amorphous alloy, the resistance of oxidation of alloy, solidity to corrosion, toughness and thermostability are slightly different.
The basic preparation process of multicomponent amorphous magnesium alloy provided by the invention is as follows: according to the alloying constituent expression formula that provides, melting in two steps prepares mother alloy, block materials melt back in the water jacketed copper crucible of vacuum arc fumace with high-melting-point constituent elements such as Cu, Ag, Ni, Y, Gd is a master alloy earlier, with the fusing point difference between reduction and the low melting point constituent element.Then, again the block materials of master alloy with low melting point elements such as Mg, Zn is positioned over, is smelted into mother alloy with the method for vacuum induction melting.The melting of each step needs repeatedly for several times, and to guarantee the even of alloying constituent, the mother alloy after the preparation after induction heating or resistive heating remelting, pours into copper mold and is cooled to room temperature again, promptly forms required block materials or component.Also can utilize squeeze casting technology to be prepared into component mother alloy.
Amorphous magnesium alloy provided by the invention, its axial compression breaking tenacity can reach 650～850 MPas.If any a small amount of pore, can cause strength degradation in the foundry goods.
In order to guarantee to form non-crystalline state by melt cooling, alloy provided by the present invention, Mg content can not be lower than 45%, can not be above 65%.Mg content outside this scope will cause alloy amorphous formation ability drop, can not obtain amorphous alloy under lower rate of cooling, can't prepare thickness surpass 3 millimeters, amorphous block material or component uniformly.Because the Mg element is easy to volatilization, in the alloy layoutprocedure, should increase (being no more than 5%) by way of compensation according to physical condition is an amount of, the deviation of composition should be no more than 1% (atomic percent).In the alloy Cu and Ag element act as the raising amorphous formation ability, total content (Cu+Ag) can not be higher than 40%, otherwise is easy to compound crystal between precipitating metal and can not forms single, uniform amorphous structure in melt cools.The effect of R in the alloy (Y, Gd, Nd, Mm) element is to improve amorphous formation ability and absorb gaseous impurities element (as oxygen), and R content can not be lower than 8%, can not surpass 15%.T (Ni, Zn, Pd) element can strengthen the amorphous formation ability of alloy, and its content is no more than 5%.X (Zr, Nb, Cr) element can provide the toughness of alloy, but the amorphous formation ability of alloy is slightly descended or weave construction inhomogeneous, and its content can not surpass 2%.
Allow to have small amount of impurities in the multicomponent amorphous magnesium alloy provided by the invention, as hydrogen, oxygen, nitrogen, carbon, phosphorus etc., impurity element mainly comes from atmosphere in parent material, the alloy smelting process, crucible material etc.The amorphous formation ability of many alloys (as zirconium base, iron-based etc.) is very responsive to the introducing of impurity, and a spot of impurity is deposited the decline that can cause alloy amorphous formation ability significantly.For example, the oxygen level in the alloy surpasses the solid solubility of oxygen, and meeting precipitating metal oxide compound phase becomes crystalline forming core particle, thereby caused the rapid decline of sloppy heat body stability, finally can't form amorphous structure in process of cooling.The principal element Mg and the rare earth (as Y, La, Ce, Nd, Sm, Gd, Mm etc.) that the invention provides alloy are very active elements; has very strong avidity with gaseous impurities elements such as oxygen; be difficult to avoid in the preparation that is introduced in alloy of impurity element and the castingprocesses; but as long as suitably control alloying constituent, the existence of a spot of magnesium oxide and rare earth oxide can guarantee that still alloy has amorphous formation ability preferably.However, the oxygen level in the alloy should not surpass 0.1% (weight percent).
According to the thermal conduction capability that copper mold contacts with melt, the rate of cooling of thin plate or pole center is minimum, and the surface cool that contacts with copper mold is the fastest.Therefore, can form uniform amorphous structure be that rate of cooling by the core place is limited to whole block materials.1 order of magnitude of the every increase of the thickness of block materials (or diameter) need form the amorphous of alloy critical cooling rate and reduce about 2 orders of magnitude.For example, be entirely the pole that amorphous thickness is approximately 1,4 and 25 millimeter, its critical cooling rate roughly is equivalent to 500,50 and 10K/ second respectively.Many common processing technologies all can reach such rate of cooling, such as, the copper mold that alloy melt is cast into the recirculated water cooling is produced piece, plate, rod or the nearly clean shape part of thickness greater than 1 millimeter non-crystalline material.The critical cooling rate of alloy amorphous formation provided by the invention (avoiding the required minimum rate of cooling of crystallization in the process of cooling) is greatly about 5～1K/ second, can adopt the method for common copper mold casting to prepare the amorphous material or the component of multiple shapes such as piece, plate, rod.Also mother alloy can be placed under the melted state not in the iron pipe that reacts with alloy melt, the molybdenum pipe (internal diameter is 0.5-3 centimetre), after vacuumizing sealing, be heated to above about 100 ℃ of alloy melting point, after the fusing evenly, quench in entry quenchants such as (or) salt solution, obtain the amorphous block material, the critical size that forms complete non-crystalline material is wanted obvious situation greater than the copper mold casting.
Description of drawings:
Fig. 1 is the as cast condition amorphous alloy pole of copper mold casting preparation,
A) diameter is the Mg of 1.6cm 54Cu 24.5Ag 10.5Y 11Alloy (embodiment 1),
B) diameter is the Mg of 2.5cm 54Cu 26.5Ag 8.5Gd 11Alloy (embodiment 4);
Fig. 2 is the x-ray diffraction pattern of seven kinds of alloy copper mold casting pole cross sections,
A) Mg 54Cu 24.5Ag 10.5Y 11, 1.6 centimetres (embodiment 1),
B) Mg 60Cu 25Ag 3Y 10Mm 2, 1.2 centimetres (embodiment 2),
C) Mg 56Cu 20Ag 11Gd 6Nd 7, 1.4 centimetres (embodiment 3),
D) Mg 54Cu 26.5Ag 8.5Gd 11, 2.5 centimetres (embodiment 4),
E) Mg 55Cu 20Ag 10Zn 3Gd 12, 1.8 centimetres (embodiment 5),
F) Mg 61Cu 14Ag 12Nd 12Zr 1, 0.8 centimetre (embodiment 6),
G) Mg 58Cu 18Ag 12Ni 2Gd 9Nb 1, 0.8 centimetre (embodiment 7);
Fig. 3 be seven kinds of alloy copper molds casting poles continuous heating DSC curve (heating rate be 20 ℃/min),
A) Mg 54Cu 24.5Ag 10.5Y 11, 1.6 centimetres (embodiment 1),
B) Mg 60Cu 25Ag 3Y 10Mm 2, 1.2 centimetres (embodiment 2),
C) Mg 56Cu 20Ag 11Gd 6Nd 7, 1.4 centimetres (embodiment 3),
D) Mg 54Cu 26.5Ag 8.5Gd 11, 2.5 centimetres (embodiment 4),
E) Mg 55Cu 20Ag 10Zn 3Gd 12, 1.8 centimetres (embodiment 5),
F) Mg 61Cu 14Ag 12Nd 12Zr 1, 0.8 centimetre (embodiment 6),
G) Mg 58Cu 18Ag 12Ni 2Gd 9Nb 1, 0.8 centimetre (embodiment 7);
Embodiment:
Embodiment 1Mg 54Cu 24.5Ag 10.5Y 11Alloy (nominal composition is an atomic percent, down together)
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Y element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Y ternary alloy become the quaternary master alloy ingot with Cu, Ag, Y master alloy with Mg element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 60 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out after in the conventional, electric-resistance stove, being heated to 580 ℃ of fusings, vert and pour in the copper mold.The geometrical shape of copper mold inner chamber is φ 16mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 16mm, long 60mm, sees Fig. 1 a.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 820 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 a.The DSC curve can be observed because Fig. 3 a is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Embodiment 2Mg 60Cu 25Ag 3Y 10Mm 2Alloy
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Y, Mm element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Y, Mm quad alloy become five yuan of master alloy ingots with Cu, Ag, Y, Mm master alloy with Mg element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 40 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out be heated to 580 ℃ of fusings in the conventional, electric-resistance stove after, upset is poured in the copper mold.The geometrical shape of copper mold inner chamber is φ 12mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 12mm, long 60mm.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 780 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 b.The DSC curve can be observed because Fig. 3 b is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Embodiment 3Mg 56Cu 20Ag 11Gd 6Nd 7Alloy
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Gd, Nd element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Gd, Nd quad alloy become five yuan of master alloy ingots with Cu, Ag, Gd, Nd master alloy with Mg element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 50 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out be heated to 580 ℃ of fusings in the conventional, electric-resistance stove after, upset is poured in the copper mold.The geometrical shape of copper mold inner chamber is φ 14mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 14mm, long 60mm.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 810 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 c.The DSC curve can be observed because Fig. 3 c is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Embodiment 4Mg 54Cu 26.5Ag 8.5Gd 11
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Gd element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Gd ternary alloy become the quaternary master alloy ingot with Cu, Ag, Gd master alloy with Mg element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 150 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out be heated to 580 ℃ of fusings in the conventional, electric-resistance stove after, upset is poured in the copper mold.The geometrical shape of copper mold inner chamber is φ 25mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 25mm, long 60mm, sees Fig. 1 b.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 840 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 d.The DSC curve can be observed because Fig. 3 d is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Embodiment 5Mg 55Cu 20Ag 10Zn 3Gd 12Alloy
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Zn, Gd element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Gd ternary alloy become five yuan of master alloy ingots with Cu, Ag, Gd master alloy with Mg, Zn element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 90 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out be heated to 580 ℃ of fusings in the conventional, electric-resistance stove after, upset is poured in the copper mold.The geometrical shape of copper mold inner chamber is φ 18mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 18mm, long 60mm.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 710 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 e.The DSC curve can be observed because Fig. 3 e is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Embodiment 6Mg 61Cu 14Ag 12Nd 12Zr 1
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Nd, Zr element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Nd, Zr quad alloy become five yuan of master alloy ingots with Cu, Ag, Nd, Zr master alloy with Mg element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 20 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out be heated to 580 ℃ of fusings in the conventional, electric-resistance stove after, upset is poured in the copper mold.The geometrical shape of copper mold inner chamber is φ 8mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 8mm, long 60mm.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 850 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 f.The DSC curve can be observed because Fig. 3 f is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Embodiment 7Mg 58Cu 18Ag 12Ni 2Gd 9Nb 1
(purity is higher than 99.5% with block materials such as the rod of commercially available pure metal Mg, Cu, Ag, Ni, Gd, Nb element, piece, ingot, plates, weight percent) is parent material, at first arc melting Cu, Ag, Ni, Gd, Nb quinary alloy become hexa-atomic master alloy ingot with Cu, Ag, Ni, Gd, Nb master alloy with Mg element material induction melting under inert atmosphere again as master alloy under the argon gas atmosphere of process titanium purifying.Master alloy ingot needs melt back for several times to guarantee the homogeneity of composition.Get 20 gram mother alloy materials and be positioned in the plumbago crucible, crucible is shifted out be heated to 580 ℃ of fusings in the conventional, electric-resistance stove after, upset is poured in the copper mold.The geometrical shape of copper mold inner chamber is φ 8mm * 60mm (can select different diameters and length or other geometrical shape as required).Melt cooling back forms the pole of diameter 8mm, long 60mm.The pole cross section is used for X-ray diffraction (XRD) analysis after mechanical polishing.Under the constant situation of other condition, changing the inner chamber geometrical shape is the copper mold of φ 4mm * 60mm, water the pole that casts out diameter 4mm, long 60mm, with the sample of low speed diamond saw from pole intercepting diameter 4mm, high 8mm, two ends are polished, be used for the test of axial compression performance, the strain rate of loading is 1 * 10 -4Second -1By the compressed rupture strength that records on the stress-strain curve is 840 MPas.The sample (about 10mg) that takes a morsel on the as cast condition pole is used for differential scanning calorimetric (DSC) to be analyzed, and heating rate is 20 ℃/minute.The XRD spectrum is dispersed the peak for typical non-crystal structure, the diffraction peak of crystal phase do not occur, illustrates that whole as cast condition pole is single amorphous phase, sees Fig. 2 g.The DSC curve can be observed because Fig. 3 g is seen in some thermopositive reaction that heat release step that glass transition causes and crystallization change cause, confirms that further cast alloy is an amorphous structure.
Table 1 alloy representative and the maximum diameter (D that under copper mold casting condition, can form even non-product attitude pole material Max)
Numbering Alloying constituent (atomic percent) D max (cm)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 26 27 Mg 60Cu 21Ag 9Y 10 Mg 60Cu 27Ag 3Y 10 Mg 56Cu 30Ag 3Y 11 Mg 50Cu 30Ag 6Y 14 Mg 54Cu 24.5Ag 10.5Y 11 Mg 60Cu 27Ag 3Gd 10 Mg 54Cu 21Ag 14Gd 11 Mg 62Cu 19Ag 8Gd 11 Mg 54Cu 26.5Ag 8.5Gd 11 Mg 54Cu 24.5Ag 10.5Gd 11 Mg 54Cu 21Ag 14Nd 11 Mg 54Cu 24.5Ag 10.5Mm 11 Mg 60Cu 27Ag 3Y 9Pd 1 Mg 54Cu 21Ag 14Gd 9Y 2 Mg 54Cu 21Ag 9Zn 4Gd 12 Mg 61Cu 14Ag 12Nd 12Zr 1 Mg 60Cu 25Ag 3Y 10Mm 2 Mg 56Cu 20Ag 11Gd 6Nd 7 Mg 55Cu 20Ag 10Zn 3Gd 12 Mg 61Cu 14Ag 12Nd 12Nb 1 Mg 57Cu 30.5Ag 0.5Nd 4Y 8 Mg 58Cu 30.5Ag 0.5Nd 1Y 10 Mg 57Cu 30.5Ag 0.5Nd 2Y 10 Mg 50Cu 22Ag 12Ni 3Gd 11.5Cr 1.5 Mg 54Cu 19Ag 12Ni 1Zn 3Gd 10Zr 1 0.8 0.8 1.4 0.8 1.6 1 2.5 0.8 2.5 2 1.2 1.2 0.9 2 2 0.8 1.2 1.4 1.8 0.6 1.6 0.9 1 0.5 1

Claims (4)

1. a class is easy to form by the casting of melt copper mold the magnesium alloy of amorphous structure, and its composition expression formula is: Mg a(Cu 1-xAg x) bR c, a wherein, b, c are atomic percent, R is at least a among element Y, Gd, Nd, the Mm (Mm is a mishmetal), a=45～65%, b=25～45%, c=8～15%, a+b+c=100%, x=0.01～0.5.
2. a class is easy to form by the casting of melt copper mold the magnesium alloy of amorphous structure, and its composition expression formula is: Mg a(Cu 1-xAg x) bT yR c, a wherein, b, c, y are atomic percent, T is at least a among element Ni, the Pd, and R is at least a among element Y, Gd, Nd, the Mm, a=45～65%, (b+y)=25～45%, c=8～15%, a+b+y+c=100%, x=0.01～0.5, y≤5%.
3. a class is easy to form by the casting of melt copper mold the magnesium alloy of amorphous structure, and its composition expression formula is: Mg a(Cu 1-xAg x) bR cX z, a wherein, b, c, z are atomic percent, R is at least a among element Y, Gd, Nd, the Mm, and X is at least a among element Zr, Nb, the Cr, a=45～65%, b=25～45%, (c+z)=8～15%, a+b+c+z=100%, x=0.01～0.5, z≤2%.
4. a class is easy to form by the casting of melt copper mold the magnesium alloy of amorphous structure, and its composition expression formula is: Mg a(Cu 1-xAg x) bT yR cX z, a wherein, b, y, c, z are atomic percent, T is at least a among element Ni, the Pd, and R is at least a among element Y, Gd, Nd, the Mm, and X is at least a among element Zr, Nb, the Cr, a=45～65%, (b+y)=25～45%, (c+z)=8～15%, a+b+y+c+z=100%, x=0.01～0.5, y≤5%, z≤2%.
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