CN102061429B - Zirconium base amorphous composite material and preparation method thereof - Google Patents
Zirconium base amorphous composite material and preparation method thereof Download PDFInfo
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- CN102061429B CN102061429B CN2009102071833A CN200910207183A CN102061429B CN 102061429 B CN102061429 B CN 102061429B CN 2009102071833 A CN2009102071833 A CN 2009102071833A CN 200910207183 A CN200910207183 A CN 200910207183A CN 102061429 B CN102061429 B CN 102061429B
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Abstract
The invention relates to a zirconium base amorphous composite material, containing a main material shown as the general formula: [(Zr1-xHfx)52Al10Cu30.5(Ni1-yFey)7.5)100-a-bYaMb, wherein x is the ratio of the atomic number of Hf to the total atomic number of Hf and Zr, and x ranges from 0 to 0.3; y is the ratio of the atomic number of Fe to the total atomic number of Fe and Ni, and y ranges from 0 to 0.3; a is the atomic percentage of Y, b is the atomic percentage of M, a is more than 0 and less than or equal to 8, and b is more than or equal to 0.01 and less than or equal to 15; M is one or more of La series metal elements, Ti, V, Nb, Ta, Cr, Mo, W, Mn and Si; and by taking the total volume of the zirconium base amorphous composite material as a reference, the content of an amorphous phase in the amorphous composite material is 50-95%, and the content of a crystalline phase is 5-50%. The zirconium base amorphous composite material provided by the invention has good comprehensive performance..
Description
Technical field
The present invention relates to a kind of amorphous composite and preparation method thereof, more specifically, the present invention relates to a kind of zirconium-base amorphous matrix material and preparation method thereof.
Background technology
Non-crystaline amorphous metal is that composed atom is that long-range is unordered, one type of novel alloy material of short range order.Because its unique microtexture, thereby have the performances such as mechanics, physics and chemistry more excellent than conventional crystalline metallic material.These superior performances make non-crystaline amorphous metal have application potential in a lot of fields.
Since earlier 1990s; Headed by the Japan and the U.S.; A series of alloying constituents have been found with strong amorphous formation ability; Wherein make the most easily with zirconium-base amorphous alloy, its critical cooling rate is in the 1K/s magnitude, can cast with method such as shrend with copper mold and be prepared into three-dimensional block materials.Recently; Having developed multicomponent again zirconium-based bulk amorphous abroad is alloy, and the distortion at room temperature of amorphous bulk matrix material is to carry out through the shear zone that forms the height localization, though the inner local plastic deformation amount of each shear zone is very big; But only there is seldom a part of shear zone to be activated in plane stress; Cause the non-crystaline amorphous metal sudden failure and do not have the generation of macroscopical viscous deformation, show as the characteristic of hard brittle material, this has just limited the use of non-crystaline amorphous metal as structured material.
According to Acta Mater (the 46th volume, the 18th phase, the 6089th page), prepare the W/Zr-Ti-Ni-Cu-Be amorphous composite through the seepage flow casting, with pure amorphous phase ratio, the adding of W can make compression plastic strain improve 9 times.In addition, according to Journal of Applied Physics (the 83rd volume, the 12nd phase; The 7993rd page); Prepare the Nb/Zr-Ti-Cu-Ni-Be amorphous composite through copper mold casting method, compare with pure non-crystalline material, compression plasticity elongation and impact value have improved 6 times and 2.5 times respectively.Yet, use expensive high purity material in the zirconium-base amorphous Composite Preparation process of developing in these prior aries, only by prepared in laboratory, be difficult to be applied to large-scale industrialization production, and its bending strength, impelling strength are not satisfactory.
Summary of the invention
It is high and be difficult to be applied to the defective that large-scale industrialization produces and provide a kind of and can be applied to large-scale industrialization production and have preferable over-all properties that the technical problem that the present invention solved is to overcome the over-all properties of zirconium-base amorphous matrix material of prior art, particularly bending strength, impelling strength is preferable and have zirconium-base amorphous matrix material of higher plastic deformation and preparation method thereof.
The invention provides a kind of zirconium-base amorphous matrix material, wherein, this zirconium-base amorphous matrix material contains the material of main part shown in following general formula:
[(Zr
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
b
Wherein, x representes the ratio of total atom number of atomicity and Hf and the Zr of Hf, and the scope of x is 0-0.3; Y representes the ratio of total atom number of atomicity and Fe and the Ni of Fe, and the scope of y is 0-0.3; A representes the atomic percent of Y, and b representes the atomic percent of M, 0＜a≤8,0.01≤b≤15; It is among metallic element, Ti, V, Nb, Ta, Cr, Mo, W, Mn and the Si one or more that M is selected from La; TV with said zirconium-base amorphous matrix material is a benchmark, and the content of the non-crystalline state phase in the said amorphous composite is 50-95%, and the content of crystalline state phase is 5-50%.
The present invention also provides a kind of preparation method of zirconium-base amorphous matrix material; Wherein, This method is included under the protection of inert gas or under the vacuum condition, the amorphous composite raw material is carried out melting and cooling forming, wherein; The raw material of said zirconium-base amorphous matrix material comprises Hf and the Fe that Zr, Al, Cu, Ni, Y and M and selectivity contain, and the add-on of each material makes the gained matrix material contain the material of main part shown in following general formula: [(Zr
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bWherein, x representes the ratio of total atom number of atomicity and Hf and the Zr of Hf, and the scope of x is 0-0.3; Y representes the ratio of total atom number of atomicity and Fe and the Ni of Fe, and the scope of y is 0-0.3; A representes the atomic percent of Y, and b representes the atomic percent of M, 0＜a≤8,0.01≤b≤15; It is among metallic element, Ti, V, Nb, Ta, Cr, Mo, W, Mn and the Si one or more that M is selected from La.
Contriver of the present invention finds, through adjusting the atomic percentage conc of each component in this zirconium-base amorphous matrix material, and in this zirconium-base amorphous matrix material, adds metal M; Can reduce the preparation requirement of this amorphous composite, the more important thing is, contriver of the present invention finds; For not only containing crystalline state mutually but also contain the matrix material of non-crystalline state phase; If not the ratio of crystalline state phase is too high, mechanical property can receive certain influence on the contrary, therefore; Through non-crystalline state in the zirconium-base amorphous matrix material is adjusted within the scope of the present invention with crystalline state ratio mutually mutually; Not only can not influence the over-all properties of zirconium-base amorphous matrix material, highly beneficial to the improvement of the comprehensive mechanical property of this matrix material on the contrary, have important practical significance for this zirconium based composite material of suitability for industrialized production.Zirconium-base amorphous matrix material provided by the invention has preferable flexural strength and higher impelling strength, and bending resistance plasticity is stronger, and the plastix strain amount can reach 3-7%; Content requirement to material purity and impurity element is lower simultaneously, allows to contain atomic percent and is less than or equal to 5% metallic impurity elements and atomic percent and is less than or equal to 1% nonmetallic impurity element.
Description of drawings
The flexural stress of the zirconium-base amorphous alloy that zirconium-base amorphous matrix material that Fig. 1 makes for embodiment 1 and Comparative Examples 1 make-strain curve figure.
Embodiment
According to the present invention, said zirconium-base amorphous matrix material contains the material of main part shown in following general formula:
[(Zr
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
b
Wherein, x representes the ratio of total atom number of atomicity and Hf and the Zr of Hf, and the scope of x can be 0-0.3; Y representes the ratio of total atom number of atomicity and Fe and the Ni of Fe, and the scope of y can be 0-0.3; A representes the atomic percent of Y, and b representes the atomic percent of M, 0＜a≤8,0.01≤b≤15; Under the preferable case, 0.1≤a≤3,0.1≤b≤5; It is among metallic element, Ti, V, Nb, Ta, Cr, Mo, W, Mn and the Si one or more that M is selected from La, and wherein, said La is that metallic element is preferably selected from one or more among Eu, Gd and the Dy.
According to the present invention; TV with said zirconium-base amorphous matrix material is a benchmark; The volume(tric)fraction of said crystalline state phase can be 5-50%, and the volume(tric)fraction of non-crystalline state phase can be 50-95%, more preferably under the situation; The volume(tric)fraction of said crystalline state phase can be 10-25%, and the volume(tric)fraction of non-crystalline state phase can be 75-90%.
Because suitability for industrialized production generally adopts the more cheap master alloy of price as raw material, thereby can make and contain some metallic element impurity in the zirconium-base amorphous matrix material that obtains, like Mg, Ca, Co etc.; And some non-metallic elements; Like C, O, N, B, P etc., still, for the present invention; The existence of a certain amount of impurity metallic elements can't influence the resulting zirconium-base amorphous performance of composites of the present invention; As: the total amount with said zirconium-base amorphous matrix material is a benchmark, and said zirconium-base amorphous matrix material can contain atomic percent and be less than or equal to 5% metallic impurity elements, and atomic percent is less than or equal to 1% nonmetallic impurity element.When foreign matter content is in the above-mentioned scope of the present invention, to the not influence of melting of zirconium-base amorphous matrix material provided by the invention.
Under the preferable case; Contriver of the present invention finds; When M be selected among Si, Ta and the Mo one or more or during for Nb and Si, Nb and Ta, Nb and Mo, Nb and Si and Ta, Nb and Si and Mo, Nb and Ta and Mo, Nb and Si and Ta and Mo, the over-all properties of zirconium-base amorphous matrix material is excellence more.The ratio of above-mentioned each material can be adjusted in relative broad range, under the preferable case, and Si and Ta, the atomic ratio of Si and Mo or Ta and Mo further is preferably 1: 0.1-5; The atomic ratio of Si, Ta and Mo further is preferably 1: 0.1-5: 0.1-5; The atomic ratio of Nb and Si, Nb and Ta, Nb and Mo can further be preferably 1: 0.1-5; The atomic ratio of Nb and Si and Ta, Nb and Si and Mo, Nb and Ta and Mo can further be preferably 1: 0.1-5: 0.1-5; The atomic ratio of Nb and Si and Ta and Mo can further be preferably 1: 0.1-5: 0.1-5: 0.1-5.
According to the present invention, the plastix strain of said zirconium-base amorphous matrix material can reach 3-7%.
The purity of various raw materials that is used to prepare zirconium-base amorphous matrix material of the present invention is preferably more than 98% weight percent as long as satisfy conventional requirement.
According to the present invention; The preparation method of said zirconium-base amorphous matrix material is included under the protection of inert gas or under the vacuum condition; The amorphous composite raw material is carried out melting and cooling forming; Wherein, the raw material of said zirconium-base amorphous matrix material comprises Hf and the Fe that Zr, Al, Cu, Ni, Y and M and selectivity contain, and the add-on of each material makes the gained matrix material contain the material of main part shown in following general formula: [(Zr
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bWherein, x representes the ratio of total atom number of atomicity and Hf and the Zr of Hf, and the scope of x is 0-0.3; Y representes the ratio of total atom number of atomicity and Fe and the Ni of Fe, and the scope of y is 0-0.3; A representes the atomic percent of Y, and b representes the atomic percent of M, 0＜a≤8,0.01≤b≤15; Under the preferable case, 0.1≤a≤3,0.1≤b≤5; It is among metallic element, Ti, V, Nb, Ta, Cr, Mo, W, Mn and the Si one or more that M is selected from La; It is benchmark that the composition of zirconium-base amorphous matrix material and the condition of cooling forming make the TV with said zirconium-base amorphous matrix material, and the content of the non-crystalline state phase in the said amorphous composite is 50-95%, is preferably 75-90%; The content of crystalline state phase is 5-50%, is preferably 10-25%.
According to the present invention, composition that can be through controlling zirconium-base amorphous matrix material according to the invention also is achieved crystalline state in the said zirconium-base amorphous matrix material of adjustment mutually and the different ratios of non-crystalline state between mutually according to the condition of the conventional method controlled chilling moulding in this area.The condition of said cooling forming comprises speed of cooling, pressure, mold material and mould thermal conductivity etc.; Wherein, Speed of cooling be in the zirconium-base amorphous matrix material crystalline state mutually with non-crystalline state one of the key factor of ratio control mutually; And the range of choice broad of conditions such as pressure, mold material and mould thermal conductivity, as long as it cooperates the speed of cooling of selecting to guarantee to obtain being fit to can satisfy described cooling forming condition.In known casting mode, the common and inversely proportional relation of speed of cooling of the volume(tric)fraction of crystalline state phase.According to the present invention, said speed of cooling can be selected in the condition and range of routine, more than 10K/s, is preferably 10
1-10
4K/s.
Wherein, It is metallic element that the M raw material can be selected zirconium-niobium alloy, silicon, chromium, manganese, vanadium, titanium, zirconium tantalum alloy, copper-tungsten, the La of cheap technical purity for use, and small amount of impurities metallic element wherein can't exert an influence to the resulting zirconium-base amorphous performance of composites of the present invention.
According to the present invention, said protection of inert gas and vacuum environment are in order to make alloy raw material in fusion process, obtain protection, to avoid oxidized.The antioxidant property of amorphous composite raw material of the present invention is better, and is therefore lower to the requirement of shielding gas atmosphere and vacuum environment.Said shielding gas is one or more in the neutral element gas in the periodic table of elements.The purity of said shielding gas is not less than 94% volume percent and gets final product, and for example can be the 94-99.9% volume percent.Feeding in the smelting furnace and only need being evacuated to vacuum tightness before the shielding gas is to get final product below 1000 handkerchiefs, be preferably less than 100 handkerchiefs, and 0.1-50 handkerchief more preferably, said vacuum tightness is represented with absolute pressure.
The method of said melting can be the melting method of various routines in this area; As long as with the abundant fusion of amorphous composite raw material, for example, can in melting equipment, carry out melting; Smelting temperature and smelting time are with raw-material different some variations that have of amorphous composite; In the present invention, smelting temperature can be 1000-3100 ℃, is preferably 1200-3000 ℃; Smelting time is as long as guarantee the abundant fusion of each component, and under the preferable case, said smelting time can be 0.5-10 minute, is preferably 1-5 minute.Said melting equipment can be the melting equipment of routine, for example vacuum arc melting furnace, vacuum induction melting furnace or vacuum resistance furnace.
The crystallized ability of zirconium-base amorphous matrix material provided by the invention is strong, and therefore, said cooling forming can adopt the pressure die casting forming method of various routines in this area, for example, fused alloy material (melt) pressure die casting in mould, is cooled off then.Said pressure die casting method can be selected from one or more in gravitational casting, negative pressure casting, malleation casting, the high-pressure casting, and casting condition can be for conventionally known to one of skill in the art like casting pressure, and for example, the pressure of high-pressure casting can be the 2-20 MPa; Wherein, said gravity casting is meant and utilizes the action of gravity of melt itself to be cast in the mould.The concrete operation method of said casting is conventionally known to one of skill in the art.For example, moulding stock can be the various die steel materials of 30-400W/mK (being preferably 50-200W/mK) for copper alloy, stainless steel and thermal conductivity.Mould can carry out water-cooled, oil cooling.
To further describe in detail the present invention through specific embodiment below.
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
With purity is that the various zirconium-base amorphous matrix material raw material of 99.7 weight % drops in the arc-melting furnace (Shenyang scientific instrument factory); With arc melting stove evacuation (vacuum tightness is 10 handkerchiefs (absolute pressures)); The argon gas that feeds purity then and be 99.9% percent by volume is as shielding gas; Under 1500 ℃, melting 3 minutes makes the abundant fusion of zirconium-base amorphous matrix material raw material; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr; Atomic percentage conc is 9.6% Al; Atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that 3% Nb and atomic percentage conc are 0.5% Y;
The method of fused sample through pressure die casting is casted into cooling forming in the copper alloy die (wherein, pressure 14MPa, moulding stock SKD61; Speed of cooling is 1000K/s); Formation is of a size of long 120 millimeters, wide 14 millimeters, thick 1 millimeter zirconium-base amorphous matrix material materials A 1; Analyze the massfraction of contained element in the alloy through inductively coupled plasma atomic emission (ICP-AES) method, be converted into atomic percent, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 1
50.2Al
9.6Cu
29.5Ni
7.2Nb
3Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.1%).
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material material; Different is; The raw material type of this zirconium-base amorphous matrix material and consumption are that atomic percentage conc is 50.8% Zr, and atomic percentage conc is 9.7% Al, and atomic percentage conc is 29.9% Cu; Atomic percentage conc is 7.3% Ni, and atomic percentage conc is that 1.5% Si and atomic percentage conc are 0.8% Y; Pressure 12MPa, moulding stock SKD61, speed of cooling is 850K/s;
The zirconium-base amorphous composite sample A2 that finally obtains; Ultimate analysis shows, this zirconium-base amorphous composite sample A2 consists of Zr
50.8Al
9.7Cu
29.9Ni
7.3Si
1.5Y
0.8(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage difference 0.05% and 0.04%).
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The raw material type of this zirconium-base amorphous matrix material and consumption are that atomic percentage conc is 50.2% Zr, and atomic percentage conc is 9.6% Al, and atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that 1.5% Cr and atomic percentage conc are 2% Y; Pressure 12MPa, moulding stock SKD61, speed of cooling is 800K/s;
Finally obtain zirconium-base amorphous composite sample A3; Ultimate analysis shows, this zirconium-base amorphous composite sample A3 consists of Zr
50.2Al
9.6Cu
29.5Ni
7.2Cr
1.5Y
2(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.08%).
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The raw material type of this zirconium-base amorphous matrix material and consumption are that atomic percentage conc is 49.4% Zr, and atomic percentage conc is 9.5% Al, and atomic percentage conc is 28.9% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that 3% Mn and atomic percentage conc are 2% Y; Pressure 12MPa, moulding stock SKD61, speed of cooling is 800K/s;
Finally obtain zirconium-base amorphous composite sample A4; Ultimate analysis shows, this zirconium-base amorphous composite sample A4 consists of Zr
49.4Al
9.5Cu
28.9Ni
7.2Mn
3Y
2(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.2%).
Embodiment 5
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The raw material type of this zirconium-base amorphous matrix material and consumption are that atomic percentage conc is 50.4% Zr, and atomic percentage conc is 9.7% Al, and atomic percentage conc is 29.6% Cu; Atomic percentage conc is 7.3% Ni, and atomic percentage conc is that 1% W and atomic percentage conc are 2% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling can be 700K/s;
Finally obtain zirconium-base amorphous composite sample A5; Ultimate analysis shows, this zirconium-base amorphous composite sample A5 consists of Zr
50.4Al
9.7Cu
29.6Ni
7.3W
1Y
2(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.1% and 0.05%).
Embodiment 6
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 46.8% Zr, and atomic percentage conc is 9% Al, and atomic percentage conc is 27.5% Cu; Atomic percentage conc is 6.7% Ni, and atomic percentage conc is that 9.5% Nb and atomic percentage conc are 0.5% Y; Pressure 20MPa, moulding stock SKD61, speed of cooling is 100K/s; In the zirconium-base amorphous matrix material that obtains, the content of crystalline state phase is 45%, and the content of non-crystalline state phase is 55%;
Finally obtain zirconium-base amorphous composite sample A6; Ultimate analysis shows, this zirconium-base amorphous composite sample A6 consists of Zr
46.8Al
9Cu
27.5Ni
6.7Nb
9.5Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.25%).
Embodiment 7
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material, and different is that the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 47.7% Zr; Atomic percentage conc is 2.5% Hf; Atomic percentage conc is 9.6% Al, and atomic percentage conc is 29.5% Cu, and atomic percentage conc is 6.8% Ni; Atomic percentage conc is 0.4% Fe, and atomic percentage conc is that 3% Nb and atomic percentage conc are 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 1000K/s;
Finally obtain zirconium-base amorphous composite sample A7; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 7
47.7Hf
2.5Al
9.6Cu
29.5Ni
6.8Fe
0.4Nb
3Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.1%).
Embodiment 8
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 5 prepares zirconium-base amorphous matrix material, and different is that the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 32.7% Zr; Atomic percentage conc is 14.1% Hf; Atomic percentage conc is 9% Al, and atomic percentage conc is 27.45% Cu, and atomic percentage conc is 5.4% Ni; Atomic percentage conc is 1.35% Fe, and atomic percentage conc is that 5% Ta and atomic percentage conc are 5% Y; Pressure 18MPa, moulding stock SKD61, speed of cooling is 700K/s;
Finally obtain zirconium-base amorphous composite sample A8; Ultimate analysis shows, this zirconium-base amorphous composite sample A8 consists of Zr
32.7Hf
14.1Al
9Cu
27.45Ni
5.4Fe
1.35Ta
5Y
5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.1%).
Embodiment 9
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material, and different is that the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr; Atomic percentage conc is 9.6% Al; Atomic percentage conc is 29.5% Cu, and atomic percentage conc is 7.2% Ni, and atomic percentage conc is 1% Si; Atomic percentage conc is 2% Ta, and atomic percentage conc is 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous composite sample A9; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 9
50.2Al
9.6Cu
29.5Ni
7.2Si
1Ta
2Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.05%).
Embodiment 10
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr, and atomic percentage conc is 9.6% Al, and atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that 3% Mo and atomic percentage conc are 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous composite sample A10; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 10
50.2Al
9.6Cu
29.5Ni
7.2Mo
3Y
0.5(wherein, metallic impurity elements and nonmetallic impurity element atomic percent are respectively 0.1% and 0.05%).
Embodiment 11
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material, and different is that the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 46.8% Zr; Atomic percentage conc is 9% Al, and atomic percentage conc is 27.45% Cu, and atomic percentage conc is 6.75% Ni; Atomic percentage conc is 1% Si; Atomic percentage conc is 3% Ta, and atomic percentage conc is 3% Mo, and atomic percentage conc is 3% Y; Pressure 20MPa, moulding stock SKD61, speed of cooling is 500K/s;
Finally obtain zirconium-base amorphous composite sample A11; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 11
46.8Al
9Cu
27.45Ni
6.75Si
1Ta
3Mo
3Y
3(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.15% and 0.1%).
Embodiment 12
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr, and atomic percentage conc is 9.6% Al, and atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that 3% Dy and atomic percentage conc are 0.5% Y; Pressure 12MPa, moulding stock SKD61, speed of cooling is 850K/s;
Finally obtain zirconium-base amorphous composite sample A12; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 12
50.2Al
9.6Cu
29.5Ni
7.2Dy
3Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.05%).
Embodiment 13
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr, and atomic percentage conc is 9.6% Al, and atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that Si and the atomic percentage conc of 2% Nb and 1% is 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous composite sample A13; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 13
50.2Al
9.6Cu
29.5Ni
7.2Nb
2Si
1Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.05%).
Embodiment 14
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr, and atomic percentage conc is 9.6% Al, and atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is that Si and 1% Ta and the atomic percentage conc of 1% Nb and 1% is 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous composite sample A14; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 14
50.2Al
9.6Cu
29.5Ni
7.2Nb
1Si
1Ta
1Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.02%).
Embodiment 15
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 1 prepares zirconium-base amorphous matrix material; Different is, the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 49.7% Zr, and atomic percentage conc is 9.5% Al; Atomic percentage conc is 29.1% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is 2% Nb and 1% Si, and 0.5% Ta and 0.5% Mo and atomic percentage conc are 0.5% Y; Pressure 15MPa, moulding stock SKD61, speed of cooling is 950K/s;
Finally obtain zirconium-base amorphous composite sample A15; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 15
49.7Al
9.5Cu
29.1Ni
7.2Nb
2Si
1Ta
0.5Mo
0.5Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.1% and 0.05%).
Embodiment 16
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 9 prepares zirconium-base amorphous matrix material, and different is that the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr; Atomic percentage conc is 9.6% Al; Atomic percentage conc is 29.5% Cu, and atomic percentage conc is 7.2% Ni, and atomic percentage conc is 2% Si; Atomic percentage conc is 1% Ta, and atomic percentage conc is 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous composite sample A16; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 16
50.2Al
9.6Cu
29.5Ni
7.2Si
2Ta
1Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.05% and 0.02%).
Embodiment 17
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 9 prepares zirconium-base amorphous matrix material, and different is that the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr; Atomic percentage conc is 9.6% Al; Atomic percentage conc is 29.5% Cu, and atomic percentage conc is 7.2% Ni, and atomic percentage conc is 0.38% Si; Atomic percentage conc is 2.62% Ta, and atomic percentage conc is 0.5% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous composite sample A17; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous matrix material materials A 17
50.2Al
9.6Cu
29.5Ni
7.2Si
0.38Ta
2.62Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.1% and 0.05%).
Embodiment 18
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 15 prepares zirconium-base amorphous matrix material; Different is, the kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 50.2% Zr, and atomic percentage conc is 9.6% Al; Atomic percentage conc is 29.5% Cu; Atomic percentage conc is 7.2% Ni, and atomic percentage conc is 0.4% Nb and 0.8% Si, and 0.8% Ta and 1% Mo and atomic percentage conc are 0.5% Y; Pressure 15MPa, moulding stock SKD61, speed of cooling is 950K/s;
Finally obtain zirconium-base amorphous composite sample A18; Ultimate analysis shows, can know the Zr that consists of of this zirconium-base amorphous composite A 18
50.2Al
9.6Cu
29.5Ni
7.2Nb
0.4Si
0.8Ta
0.8Mo
1Y
0.5(wherein, metallic impurity elements and nonmetallic impurity elements atomic percentage are respectively 0.1% and 0.05%).
Embodiment 19
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 3 prepares zirconium-base amorphous matrix material, and different is, pressure is 9MPa, moulding stock SKD61, and speed of cooling is 600K/s; Crystalline state and non-crystalline state ratio mutually in the zirconium-base amorphous matrix material that obtains with change obtain zirconium-base amorphous composite A 19.
Embodiment 20
Present embodiment is explained zirconium-base amorphous matrix material [(Zr provided by the invention
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bPreparation.
Method according to embodiment 3 prepares zirconium-base amorphous matrix material, and different is, pressure is 7MPa, moulding stock SKD61, and speed of cooling is 520K/s; Crystalline state and non-crystalline state ratio mutually in the zirconium-base amorphous matrix material that obtains with change, zirconium-base amorphous composite A 20.
Comparative Examples 1
The preparation of the zirconium-base amorphous alloy of this Comparative Examples explanation prior art.
Method according to embodiment 1 prepares zirconium-base amorphous alloy; Different is; The kind of this zirconium-base amorphous alloy raw material and consumption are that atomic percentage conc is 50.9% Zr; Atomic percentage conc is 9.8% Al, and atomic percentage conc is 29.9% Cu, and atomic percentage conc is that 7.4% Ni and atomic percentage conc are 2% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 1000K/s;
Finally obtain zirconium-base amorphous alloy sample C1; Ultimate analysis shows, this zirconium-base amorphous alloy sample C1 consists of Zr
50.9Al
9.8Cu
29.9Ni
7.4Y
2
Comparative Examples 2
The preparation of the zirconium-base amorphous matrix material of this Comparative Examples explanation prior art.
The method of describing according to Journal of Applied Physics in the background technology (the 83rd volume, the 12nd phase, the 7993rd page) prepares.The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 56.2% Zr; Atomic percentage conc is 13.8% Ti; Atomic percentage conc is 6.9% Cu; Atomic percentage conc is 5.6% Ni, and atomic percentage conc is that 5% Nb and atomic percentage conc are 12.5% Be, and adopts the copper mold casting method moulding.
Finally obtain zirconium-base amorphous alloy sample C2; Ultimate analysis shows, this zirconium-base amorphous composite sample C2 consists of Zr
56.2Ti
13.8Cu
6.9Ni
5.6Nb
5Be
12.5
Comparative Examples 3
The preparation of the zirconium-base amorphous alloy of this Comparative Examples explanation prior art.
With purity is that the various zirconium-base amorphous matrix material raw material of 99.7 weight % drops in the arc-melting furnace (Shenyang scientific instrument factory); With arc melting stove evacuation (vacuum tightness is 10 handkerchiefs (absolute pressures)); The argon gas that feeds purity then and be 99.9% percent by volume is as shielding gas; Under 1500 ℃, melting 3 minutes makes the abundant fusion of zirconium-base amorphous matrix material raw material; The kind of this zirconium-base amorphous matrix material raw material and consumption are that atomic percentage conc is 55% Zr; Atomic percentage conc is 2% Ti; Atomic percentage conc is 9.6% Al; Atomic percentage conc is 16.5% Cu, and atomic percentage conc is 13.5% Ni, and atomic percentage conc is that 3% Nb and atomic percentage conc are 0.4% Y; Pressure 14MPa, moulding stock SKD61, speed of cooling is 900K/s;
Finally obtain zirconium-base amorphous alloy sample C3; Ultimate analysis shows, this zirconium-base amorphous alloy sample C3 consists of Zr
55Ti
2Al
9.6Cu
16.5Ni
13.5Nb
3Y
0.4
Embodiment 21-40
Present embodiment is used to explain the qualitative analysis and the performance test of zirconium-base amorphous matrix material provided by the invention
1, metallographic microanalysis
The composite sample that the foregoing description 1-20 is made carries out grinding and polishing respectively on model is the metal grinding polishing machine of MP-1B, to judge the volume(tric)fraction of matrix non-crystalline state phase in the matrix material.Utilize granularity to be respectively the conventional silit waterproof abrasive paper of 600#, 800#, 1000#, 1500#, 2000# and grind successively, again through the polishing of diamond polishing cream.Through amorphous composite etching reagent corrosion sample surfaces, utilize Leica DM2000 metallography microscope sem observation embodiment sample surfaces pattern and calculate the wherein volume(tric)fraction of amorphous phase again, the volume(tric)fraction of each embodiment sample matrices amorphous phase of mensuration is as shown in table 1.
2, anti-reflecting bending strength determining
The zirconium-base amorphous composite sample that the foregoing description 1-20 makes is tested as follows: the sheet material that the sample intercepting is become 100mm * 14mm * 1mm; Utilize the three-point bending fracture intensity of CMT5105 electronic universal tester specimen, the result is as shown in table 1 for the bending strength of each embodiment sample of mensuration, bending resistance plasticity.
In addition, the three-point bending stress-strain curve of the zirconium-base amorphous composite sample A1 that is prepared by embodiment 1 is as shown in Figure 1, as can be seen from Figure 1, has significantly level and smooth stage curve, explains to have bending resistance plasticity platform.
3, impelling strength is measured
The zirconium-base amorphous composite sample that the foregoing description 1-20 makes is tested as follows: the sheet material that each sample intercepting is become 3mm * 14mm * 1mm; Utilize the impelling strength of ZBC50 balance weight impact testing machine specimen, the result of the notched bar impact strength of each embodiment sample of mensuration is as shown in table 1.
Comparative Examples 4-6
This Comparative Examples is used to explain qualitative analysis and the performance test by the zirconium-base amorphous matrix material of existing method preparation.
Method according to embodiment 21-40 is tested alloy sample, and different is, test be the alloy sample C1-C3 that the method by Comparative Examples 1-3 prepares.
The three-point bending stress-strain curve of the zirconium-base amorphous alloy sample C1 that is prepared by Comparative Examples 1 is as shown in Figure 1.By finding out among Fig. 1, sample C1 does not have tangible plasticity platform, is ready-made typical brittle rupture characteristic.
Other test result is as shown in table 1.
Table 1
| Sample number into spectrum | Amorphous phase ratio (%) | Bending strength (MPa) | Plastix strain amount ε p (％) | Impelling strength (KJ/m 2) |
| A1 | 90 | 2248 | 3 | 100.81 |
| A2 | 95 | 2308 | 4 | 92.35 |
| A3 | 94 | 2365 | 3.5 | 77.39 |
| A4 | 94 | 2280 | 3.5 | 98.55 |
| A5 | 95 | 2490 | 5 | 100.13 |
| A6 | 55 | 2192 | 4 | 80.55 |
| A7 | 90 | 2315 | 3.5 | 98.03 |
| A8 | 70 | 2197 | 4 | 82.36 |
| A9 | 85 | 2453 | 5 | 106.36 |
| A10 | 90 | 2370 | 5 | 100.53 |
| A11 | 75 | 2290 | 5 | 94.56 |
| A12 | 92 | 2398 | 4.5 | 95.94 |
| A13 | 90 | 2235 | 3 | 85.76 |
| A14 | 90 | 2513 | 5 | 112.38 |
| A15 | 85 | 2462 | 4.5 | 109.85 |
| A16 | 85 | 2455 | 5 | 105.45 |
| A17 | 70 | 2237 | 3 | 80.21 |
| A18 | 83 | 2430 | 4.5 | 105.57 |
| A19 | 85 | 2415 | 4.5 | 85.68 |
| A20 | 70 | 2365 | 5 | 79.88 |
| C1 | 100 | 2488 | 0 | 52.48 |
| C2 | 75 | 2157 | 2 | 58.56 |
| C3 | 100 | 2376 | 0 | 46.23 |
Result from last table 1 can find out that all more than 2190MPa, impelling strength is all at 77MJ/m for the bending strength of the zirconium-base amorphous matrix material that the method for employing embodiment of the invention 1-20 makes
2More than; And the bending strength of the amorphous composite C2 that is made by Comparative Examples 2 is relatively poor, and plasticity is merely 2%; Though non-crystaline amorphous metal sample C1, C3 bending strength by Comparative Examples 1 and Comparative Examples 3 make are also better, its basic non-plastic, in addition, the impelling strength of sample C1-C3 is the highest less than 60MJ/m
2Explanation thus; Compare with the zirconium-base amorphous alloy and the zirconium-base amorphous matrix material of prior art; Zirconium-base amorphous matrix material provided by the invention has excellent comprehensive performances and wide in range preparation restriction; Greatly reduced production cost, had important practical significance for the large-scale industrialization production of zirconium-base amorphous matrix material.
Claims (11)
1. a zirconium-base amorphous matrix material is characterized in that, this zirconium-base amorphous matrix material contains the material of main part shown in following general formula:
[(Zr
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
b
Wherein, x representes the ratio of total atom number of atomicity and Hf and the Zr of Hf, and the scope of x is 0-0.3; Y representes the ratio of total atom number of atomicity and Fe and the Ni of Fe, and the scope of y is 0-0.3; A representes the atomic percent of Y, and b representes the atomic percent of M, 0＜a≤8,0.01≤b≤15; It is among metallic element, Ti, V, Nb, Ta, Cr, Mo, W, Mn and the Si one or more that M is selected from La; TV with said zirconium-base amorphous matrix material is a benchmark, and the content of the non-crystalline state phase in the said amorphous composite is 50-95%, and the content of crystalline state phase is 5-50%.
2. zirconium-base amorphous matrix material according to claim 1, wherein, 0.1≤a≤3,0.1≤b≤5.
3. zirconium-base amorphous matrix material according to claim 1, wherein, M be selected among Si, Ta and the Mo one or more or for Nb and Si, Nb and Ta, Nb and Mo, Nb and Si and Ta, Nb and Si and Mo, Nb and Ta and Mo, Nb and Si and Ta and Mo.
4. zirconium-base amorphous matrix material according to claim 1 wherein, is a benchmark with the TV of said zirconium-base amorphous matrix material, and the content of the non-crystalline state phase in the said amorphous composite is 75-90%, and the content of crystalline state phase is 10-25%.
5. zirconium-base amorphous matrix material according to claim 1; Wherein, Total amount with said zirconium-base amorphous matrix material is a benchmark; Said zirconium-base amorphous matrix material also contains atomic percent and is less than or equal to 5% metallic impurity elements, and atomic percent is less than or equal to 1% nonmetallic impurity element.
6. zirconium-base amorphous matrix material according to claim 1, wherein, the plastix strain of said zirconium-base amorphous matrix material is 3-7%.
7. the preparation method of the said zirconium-base amorphous matrix material of claim 1; This method is included under the protection of inert gas or under the vacuum condition; The raw material of zirconium-base amorphous matrix material is carried out melting and cooling forming; It is characterized in that the raw material of said zirconium-base amorphous matrix material comprises Hf and the Fe that Zr, Al, Cu, Ni, Y and M and selectivity contain, the add-on of each material makes the gained matrix material contain the material of main part shown in following general formula: [(Zr
1-xHf
x)
52Al
10Cu
30.5(Ni
1-yFe
y)
7.5]
100-a-bY
aM
bWherein, x representes the ratio of total atom number of atomicity and Hf and the Zr of Hf, and the scope of x is 0-0.3; Y representes the ratio of total atom number of atomicity and Fe and the Ni of Fe, and the scope of y is 0-0.3; A representes the atomic percent of Y, and b representes the atomic percent of M, 0＜a≤8,0.01≤b≤15; It is among metallic element, Ti, V, Nb, Ta, Cr, Mo, W, Mn and the Si one or more that M is selected from La; It is benchmark that the composition of zirconium-base amorphous matrix material and the condition of cooling forming make the TV with said zirconium-base amorphous matrix material, and the content of the non-crystalline state phase in the said amorphous composite is 50-95%, and the content of crystalline state phase is 5-50%.
8. method according to claim 7, wherein, 0.1≤a≤3,0.1≤b≤5.
9. method according to claim 7, wherein, M be selected among Si, Ta and the Mo one or more or for Nb and Si, Nb and Ta, Nb and Mo, Nb and Si and Ta, Nb and Si and Mo, Nb and Ta and Mo, Nb and Si and Ta and Mo.
10. method according to claim 7 wherein, is a benchmark with the TV of said zirconium-base amorphous matrix material, and the content of the non-crystalline state phase in the said amorphous composite is 75-90%, and the content of crystalline state phase is 10-25%.
11. method according to claim 7, wherein, the method for said cooling forming is selected from one or more in gravitational casting, negative pressure casting, malleation casting and the high-pressure casting; The condition of said cooling forming comprises that speed of cooling is 10
1-10
4K/s.
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| CN102912262B (en) * | 2012-11-09 | 2014-10-15 | 湖南科技大学 | Zirconium-based endogenous-phase amorphous composite material and preparation method for same |
| CN103938132B (en) * | 2013-08-22 | 2016-07-06 | 中国科学院金属研究所 | A kind of zirconium-base amorphous alloy with strong glass forming ability |
| CN103484800B (en) * | 2013-09-10 | 2015-12-09 | 黄利敏 | A kind of zirconium-base amorphous alloy and preparation method thereof |
| CN104878328B (en) * | 2014-09-29 | 2016-10-05 | 中国科学院金属研究所 | Structure-controllable TiZr base amorphous composite material and preparation thereof |
| CN105112817B (en) * | 2015-09-10 | 2017-03-29 | 深圳市锆安材料科技有限公司 | A kind of non-crystaline amorphous metal of wear-and corrosion-resistant and preparation method thereof |
| CN105220083B (en) * | 2015-10-21 | 2017-05-31 | 东莞宜安科技股份有限公司 | A kind of non-crystaline amorphous metal of wear-and corrosion-resistant and its preparation method and application |
| CN105239024A (en) * | 2015-11-13 | 2016-01-13 | 东莞宜安科技股份有限公司 | High-hardness amorphous composite as well as preparation method and application thereof |
| CN108385039B (en) * | 2018-02-07 | 2021-01-01 | 瑞声精密制造科技(常州)有限公司 | Additional high-toughness zirconium-based amorphous composite material and preparation method thereof |
| CN108193147B (en) * | 2018-02-07 | 2020-11-27 | 瑞声精密制造科技(常州)有限公司 | High-toughness zirconium-based amorphous alloy material and preparation method thereof |
| CN109957732B (en) * | 2019-04-08 | 2020-11-27 | 东北大学 | Method for continuously preparing zirconium-based amorphous thin strip |
| CN115354246B (en) * | 2022-08-24 | 2023-05-09 | 盘星新型合金材料(常州)有限公司 | Rare earth modified light block amorphous alloy and preparation method and application thereof |
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| EP1416061B1 (en) * | 2002-10-31 | 2008-05-07 | Howmet Research Corporation | Tantalum modified amorphous alloy |
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Effective date of registration: 20191230 Address after: 314411 Jianshe East Road, Guodian, Yanguan Town, Haining City, Jiaxing City, Zhejiang Province Patentee after: Haining Yanguan Industrial Investment Co., Ltd Address before: 518118, Ping Ping Road, Pingshan Town, Longgang District, Guangdong, Shenzhen 3001 Patentee before: Biyadi Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121121 Termination date: 20201113 |