CN1274867C - Cu-Zr-Nb series block non crystalline alloy - Google Patents
Cu-Zr-Nb series block non crystalline alloy Download PDFInfo
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- CN1274867C CN1274867C CN 200410021060 CN200410021060A CN1274867C CN 1274867 C CN1274867 C CN 1274867C CN 200410021060 CN200410021060 CN 200410021060 CN 200410021060 A CN200410021060 A CN 200410021060A CN 1274867 C CN1274867 C CN 1274867C
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Abstract
The present invention relates to a bulk amorphous alloy of a Cu-Zr-Nb series, which belongs to the new material field and comprises a Cu element and a Zr element. The present invention is characterized in that few Nb elements are contained. A general formula is (Cu<x>Zr<1-x>) <1-y>Nb<y>, wherein the x is larger or equal to 40 wt. % and is smaller or equal to 65 wt. %, and the y is larger or equal to 1 wt. % or smaller or equal to 15 wt. %. Technology: under the protection of argon gas, Zr and Nb pure metals are melted under the temperature of 2800K to 3200K and the current density of 150 A/cm<2> to 170 A/cm<2> by a non-consumable arc-melting method. After proper temperature is reached, smelting is continued for 10 seconds and power is switched off. When room temperature is reached by cooling, a mixed metal is turned over and is put in a water cooled copper crucible for smelting for the second time. Smelting is carried out for many times to form the pre-alloy of Zr (Nb). Then, the pre-alloy of Zr (Nb) is mixed with the Cu element. Smelting temperature is from 2000K to 2800K, and current density is from 120 A/cm<2> to 150 A/cm<2>. The alloy of Cu-Zr-Nb is evenly prepared. Finally, a negative-pressure suction casting method with a copper mould is carried out. A non crystal bar is obtained by suction casting, and the difference of air pressure is from 0.01 to 0.02MPa during suction casting. The present invention has the advantages that the glass-forming ability of the alloy of Cu-Zr-Nb series is strong, thermal stability is high, and hardness and yield strength are high.
Description
Technical field
The present invention relates to a kind of preparation, belong to field of new with Cu-Zr-Nb alloy of strong amorphous formation ability.
Background technology
Amorphous metal alloy is the metal or alloy that a class has short range order, long-range disordered structure feature, and they have very high comprehensive mechanical property and unique physical and chemical performance.Yet because the influence of metal or alloy amorphous formation ability (promptly forming the ability of amorphous alloy) prepares the higher rate of cooling of such material require, general critical cooling rate is 10
5K/s.With cooling rate is preface from high to low, and chilling technique commonly used has: melt atomizing, film deposition techniques and copper roller chilling get rid of the band machine technology, and material shape often is low-dimensional materials such as powder, strip etc., and therefore its range of application is very limited.
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 be easy to the most make with the Zr base, its critical cooling rate is only in the 1K/s magnitude, can cast and method such as shrend is prepared into three-dimensional block materials with copper mold, be called as block amorphous alloy.Block amorphous alloy not only has more traditional low-dimensional non-crystaline amorphous metal more excellent machinery and physical and chemical performance, and simultaneously, owing to broken through the size constraint, they have the possibility as structured material.In addition, can realize accurate rapid shaping in this class material is between its supercooling liquid phase region, this favorable manufacturability can further have been expanded its range of application.At present, beautiful, day two countries are used for golf club and armor-piercing head with the Zr base block amorphous alloy, obtain enormous benefits.Recently, developed the base block amorphous system of multicomponent Cu abroad again, with respect to non-crystaline amorphous metals such as Zr base, Pd bases, Cu is base block amorphous to have higher intensity and cheap price, and more practical value is arranged.At present, known Cu base block amorphous alloy all is that (this system only can form and get rid of the band amorphous in Cu-Zr binary amorphous architectonical, can not form bulk amorphous alloy) the basis on, new constituent element grows up by adding, as Cu-Ti-Zr and Cu-Ti-Zr-Ni etc., but often there is the crystal of a large amount of nanoscales to exist mutually in these alloys, influenced the overall performance (as solidity to corrosion etc.) of Cu base block amorphous alloy.Metal Nb is the alloying element that effectively improves Zr alloy amorphous formation ability of base and thermostability.But owing to Cu-Nb is reasons such as complete immiscible system, the high-melting-point element nb is difficult to be alloyed into fully in the Cu-Zr alloy, and so far, people also fail to obtain to have the Cu-Zr-Nb alloy of strong amorphous formation ability.
Summary of the invention
The objective of the invention is to overcome refractory metal Nb and be difficult to be melted to fully a difficult problem in the Cu-Zr alloy, and the uniform Cu-Zr-Nb alloy of a kind of prepared composition method is provided, release the series bulk amorphous alloy of Cu-Zr-Nb with high amorphous formation ability.
Realize that thinking of the present invention is; utilize Zr, Nb element can form the characteristics of the substitutional solid solution that dissolves each other fully at high temperature; under the argon gas atmosphere protection; the proceed step by step melting; by non-consumable arc melting method melting Zr, Nb pure metal raw material under the temperature that is higher than pure Nb fusing point; obtain the relatively low Zr of fusing point (Nb) prealloy ingot, realize dissolving each other fully of Zr-Nb element, and effectively reduce the fusing point of Zr and Nb constituent element.Then Zr (Nb) prealloy ingot is mixed with pure Cu metal charge, carry out repeatedly melting with the non-consumable arc melting method again, obtain the uniform Cu-Zr-Nb alloy of composition, use copper mold negative pressure suction casting method at last, prepare the series bulk amorphous alloy of Cu-Zr-Nb.Whole process is by argon shield.
The series bulk amorphous alloy of Cu-Zr-Nb proposed by the invention comprises Cu element and Zr element, it is characterized in that: also include minor N b element; The composition general formula of the series bulk amorphous alloy of Cu-Zr-Nb (weight percent wt.%, down together) scope is: (Cu
xZr
1-x)
1-yNb
y, wherein, the span of x is: 40wt.%≤x≤65wt.%, and the span of y is: 1wt.%≤y≤15wt.%.
The processing method for preparing the series bulk amorphous alloy of Cu-Zr-Nb proposed by the invention, comprise composition proportion weighing, Heating temperature, fusion process and speed of cooling, it is characterized in that: proceed step by step is answered in melting, comprises melting to Zr (Nb) prealloy ingot, to the melting of Cu-Zr-Nb alloy pig and the preparation of Cu-Zr-Nb block amorphous alloy; Its processing step is:
The first step is got the raw materials ready
Take by weighing the value of each constituent element by the weight percent of design mix, the purity requirement of Cu, Zr, Nb raw metal is 99%, and with Zr, Nb metal charge mixing for standby use;
Second step, the melting of Zr (Nb) prealloy ingot
The compound of Zr and Nb metal is placed in the water jacketed copper crucible of arc-melting furnace; adopt the non-consumable arc melting method under the protection of argon gas, to carry out melting; temperature is 2800K～3200K; measure melt temperature by infrared thermometer; and control smelting temperature by adjusting current density, the span of control of current density is: 150A/cm
2～170A/cm
2, cut off the power supply after continuing 10 seconds of melting to temperature back, allow alloy be cooled to room temperature with copper crucible, then with its upset, place again in the water jacketed copper crucible, carry out melting second time, melt back like this repeatedly obtains the uniform Zr of composition (Nb) prealloy ingot;
The 3rd step, the melting of Cu-Zr-Nb alloy pig
The Cu raw material is mixed with Zr (Nb) prealloy ingot; adopt the non-consumable arc melting method under the protection of argon gas, to carry out melting; smelting temperature is 2000K～2800K; measure melt temperature by infrared thermometer; and control smelting temperature by adjusting current density, the span of control of current density is: 120A/cm
2～150A/cm
2, cut off the power supply after continuing 10 seconds of melting to temperature back, allow alloy be cooled to room temperature with copper crucible, then with its upset, place again in the water jacketed copper crucible, carry out melting second time, melt back like this repeatedly obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 4th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, under argon shield,, measure melt temperature by infrared thermometer, and pass through 120A/cm with non-consumable arc melting method molten alloy
2～150A/cm
2Current density control melt temperature, smelting temperature is 2000K～2800K, cuts off the power supply after continuing 10 seconds of melting to temperature back, opens the negative pressure absorbing and casting device simultaneously, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains block amorphous alloy.
Ar pressure in of the present invention being further characterized in that, arc-melting furnace is 0.02MPa～0.04MPa; Obtaining diameter by copper mold negative pressure suction casting method is the non-crystaline amorphous metal rod of 3mm, and its critical cooling velocity is 10
3～10
2K/s; Draught head when the copper mold negative pressure is inhaled casting is 0.01MPa～0.02MPa.
The solution of the present invention is according to the sub-concentration line of the power transformation of multicomponent alloy phase criterion, and promptly the multicomponent alloy phase and phase closes the relation criterion of subgroup unit system phase, design Cu-Zr-Nb alloying constituent.Adopt non-consumable arc-melting furnace and copper mold negative pressure to inhale casting machine, by the uniform Cu-Zr-Nb alloy of the processing method prepared composition that proposes in the thinking of the present invention.With X-ray diffractometer, differential scanning calorimeter (Mettler DSC822
e) and differential thermal analyzer (Mettler TGA/SDTA851
e) analyze and measure the structure and the thermodynamical coordinate of Cu-Zr-Nb alloy, the composition range of determining the Cu-Zr-Nb block amorphous alloy with strong amorphous formation ability is (Cu
xZr
1-x)
1-yNb
y, wherein, the span of x is: 40wt.%≤x≤65wt.%; And the span of y is: 1wt.%≤y≤15wt.%.The preparation technology parameter of the Cu-Zr-Nb block amorphous alloy of heterogeneity is different.On the one hand, the proportioning of Cu, Zr element constant (being one timing of x value) in alloy, along with the increase of Nb content in the alloy when 1wt.% changes to 15wt.% (be y value from), the temperature of melting Zr (Nb) prealloy ingot will be brought up to 3200K from 2800K and (realize that by the control current density value current density is from 150A/cm
2Rise to 170A/cm
2), the whole smelting temperature of Cu-Zr-Nb alloy then drops to 2000K from 2800K, and (current density is from 150A/cm
2Reduce to 120A/cm
2), simultaneously, the draught head when the copper mold negative pressure is inhaled casting also is increased to 0.02MPa from 0.01MPa accordingly.On the other hand, when one timing (being that y gets the determined value between 1wt.% to 15wt.%) of the Nb content in the alloy, along with Cu in the alloy: the increase of Zr element proportioning (be Cu wt.%: Zrwt.% increased to 65: 35 from 40: 60), the smelting temperature of Zr (Nb) prealloy ingot will progressively reduce, and variation range is: (current density is from 170A/cm for 3200～2800K
2Change to 150A/cm
2), simultaneously, the smelting temperature of Cu-Zr-Nb alloy also progressively reduces, and variation range is: (current density is from 150A/cm for 2800～2000K
2Change to 120A/cm
2).Draught head when accordingly, the copper mold negative pressure is inhaled casting is reduced to 0.01MPa with the reduction of alloy melting temp from 0.02MPa.
The X-ray diffraction result of Cu-Zr-Nb alloy shows, is (the Cu of 3mm at diameter
53Zr
47)
1-yNb
yIn the series alloy rod, if Nb content is during less than 1wt.% or greater than 15wt.%, a large amount of bright and sharp diffraction peaks will appear in the X-ray diffraction spectrum of alloy, show and generated a large amount of crystal phases in the alloy, and when the Nb content in the alloy is in 1wt.% to 15wt.% scope, the X-ray diffraction spectrum of alloy bar all presents typical non-crystalline state diffractive features, shows that they are block amorphous alloys.Finally, experiment is determined: at (Cu
xZr
1-x)
1-yNb
y(40wt.%≤x≤65wt.%; In the composition range of 1wt.%≤y≤15wt.%), all can obtain the non-crystal bar of diameter 3mm by copper mold casting.Wherein, typical composition Cu
46.4Zr
52.3Nb
1.3, Cu
45.8Zr
51.7Nb
2.5And Cu
45.2Zr
51.0Nb
3.8The amorphous quality of alloy is analyzed DSC, DTA Experimental Characterization by heat, and relevant amorphous stability that records and the experimental data that forms ability are with being listed in the table 1.
T
g, T
xBe the characteristic parameter that characterizes the non-crystaline amorphous metal thermostability, its value increase shows the anti-crystallization ability reinforcement of amorphous, and the thermostability of amorphous is increasing.Table 1 shows, along with the Nb element a small amount of (≤15wt.%) add, Cu-Zr-Nb is that the thermostability of non-crystaline amorphous metal strengthens afterwards earlier and weakens.Wherein, the non-crystaline amorphous metal with optimal heat stability is Cu
45.2Zr
51.0Nb
3.8And the supercooling liquid phase region Δ T of four kinds of alloys
xBe worth basic identical, all near 30K.
Reduction glass transformation temperature T
Rg=T
g/ T
lIt is the significant parameter that characterizes amorphous formation ability.The T of four Cu-Zr-Nb block amorphous alloys in the table 1
lBe worth basic identical because Nb content is the T of the non-crystaline amorphous metal of 3.8wt.%
gBe worth higherly, corresponding, its reduction glass transformation temperature is bigger, T
g/ T
lBe 0.599.Similarly, at the parameter γ (γ=T of the sign amorphous formation ability that proposes recently
x/ (T
g+ T
l)) the value aspect, Nb content is that the non-crystaline amorphous metal of 3.8wt.% also has maximum value 0.390.Therefore, Nb content is that the amorphous formation ability of non-crystaline amorphous metal of 3.8wt.% is the highest relatively.
The test of room temperature density and hardness finds that the series bulk amorphous alloy density of Cu-Zr-Nb is close, but their vickers hardness number is along with the content of Nb is obvious.When Nb content in the alloy when 1.3wt.% is increased to 3.8wt.%, the Vickers' hardness of block amorphous alloy is from 587 (kg/mm
2) be reduced to 566.Wherein, Cu
46.4Zr
52.3Nb
1.3Hardness value reach 587, be higher than in the Cu-Zr-Ti system that Inoue finds preferably composition Cu
54.3Zr
38.9Ti
6.8Hardness value (Hv=567 measures under same test conditions), other two hardness of alloy and Cu
54.3Zr
38.9Ti
6.8Alloy phase with.Formula σ rule of thumb
y=3Hv can estimate the yield strength of alloy, all above 1700MPa.
By above-mentioned experimental analysis, can draw following result: the alloy smelting process method that proposes by the present invention, can the uniform Cu-Zr-Nb alloy of successful prepared composition; The Nb element can effectively improve the amorphous formation ability of Cu-Zr base alloy; General, can only obtain getting rid of the band amorphous in the Cu-Zr two component system, (≤15wt.%) interpolation is at (the Cu of Cu-Zr-Nb alloy system because small amount of N b
xZr
1-x)
1-yNb
y(40wt.%≤x≤65wt.%; In the composition range of 1wt.%≤y≤15wt.%), all can obtain the non-crystal bar of diameter 3mm by copper mold casting; By experimental formula T
c(K/s)=10/R
2(cm) (T
cBe critical cooling velocity, R is that the maximum of non-crystaline amorphous metal forms thickness) can to estimate the critical cooling velocity that forms the Cu-Zr-Nb non-crystaline amorphous metal be 10
3～10
2The K/s magnitude, than low 2～3 orders of magnitude of the critical cooling rate that forms the Cu-Zr non-crystaline amorphous metal, this shows that the interpolation of Nb has improved more than 100 times the amorphous formation ability of Cu-Zr alloy.
Advantage of the present invention is: 1. owing to adopted first melting Zr (Nb) prealloy, the processing method of the substep melting of melting Cu-Zr-Nb alloy has realized the fusion fully of Nb element and Zr, Cu metal again, thereby obtains the uniform Cu-Zr-Nb alloy of composition; 2. because element nb adds, it effectively raises the amorphous formation ability of Cu-Zr alloy, at (Cu
xZr
1-x)
1-yNb
y(wherein, the value of x is: 40wt.%≤x≤65wt.%; The value of y is: in the scope of 1wt.%≤y≤15wt.%), all available common copper mold casting is prepared the Cu-Zr-Nb non-crystaline amorphous metal rod that diameter is 3mm, and its critical cooling velocity that forms amorphous is 10
3～10
2The K/s magnitude, low 2～3 orders of magnitude of critical cooling rate than CuZr non-crystaline amorphous metal show that the interpolation of Nb has improved more than 100 times the amorphous formation ability of Cu-Zr alloy; 3. because refractory metal Nb can improve the thermostability of non-crystaline amorphous metal, and simultaneously, Nb is the effective element of reinforced alloys, therefore, the Cu-Zr-Nb block amorphous alloy all has high thermostability and high physical strength, its crystallization temperature T
xAll above 700K, its room temperature Vickers hardness surpasses 570, and yield strength surpasses 1700MPa.
The subordinate list explanation
Table 1 is the typical composition and the characteristic temperature measuring result of Cu-Zr-Nb block amorphous alloy.T
gThe expression second-order transition temperature, T
xCrystallization temperature, supercooling liquid phase region Δ T
x, T
lLiquidus point, T
g/ T
lThe reduction glass transformation temperature, parameter γ is defined as: T
x/ (T
g+ T
l).The result shows: the Cu-Zr-Nb block amorphous alloy all has high thermostability and strong amorphous formation ability.Wherein, having optimal heat non-crystaline amorphous metal stable and amorphous formation ability is Cu
45.2Zr
51.0Nb
3.8
Table 2 is comparisons of room temperature density p, hardness Hv and the yield strength σ y of Cu-Zr-Nb block amorphous alloy and other Cu base noncrystal alloy.The result shows: the series bulk amorphous alloy of Cu-Zr-Nb all has higher hardness and intensity.Wherein, Cu
46.4Zr
52.3Nb
1.3Vickers hardness number be 587, be higher than in the Cu-Zr-Ti system that Inoue finds preferably composition Cu
54.3Zr
38.9Ti
6.8, its yield strength is 1760MPa.
Embodiment
Below in conjunction with subordinate list, describe the embodiment of the series bulk amorphous alloy of Cu-Zr-Nb in detail, existing with composition Cu
46.4Zr
52.3Nb
1.3, Cu
45.2Zr
51.0Nb
3.8, Cu
39.7Zr
44.8Nb
15.5, Cu
44.1Zr
49.8Nb
6.1And Cu
42.2Zr
47.6Nb
10.2Be example, the preparation process of the series bulk amorphous alloy of Cu-Zr-Nb is described.And, thermodynamics characteristics and performance characteristic that Cu-Zr-Nb is series bulk amorphous are described in conjunction with subordinate list.
Embodiment one, Cu
46.4Zr
52.3Nb
1.3Block amorphous alloy preparation and performance test thereof
The first step, the selection of alloying constituent
According to Cu-Zr two component system alloy phase diagram feature, the rich Cu district (40≤Cuwt.%≤65) in getting rid of band amorphous formation district chooses eutectic point (as Cu
47Zr
53Deng), the optimal components point of Cu base amorphous in the acquisition Cu-Zr two component system selects Nb as another constituent element, connects Cu
56Zr
44Eutectic point and the 3rd constituent element Nb make up the sub-concentration line of power transformation.Along Cu
47Zr
53The sub-concentration line design of-Nb power transformation alloying constituent (weight percent) is as Cu
46.4Zr
52.3Nb
1.3
Second step, the weighing of composition proportion
According to the alloying constituent of design, weighing purity in proportion is 99% high pure metal Zr, Nb and Cu raw material, and wherein, the amount of Cu is 46.4%, and the amount of Zr is 52.3%, and the amount of Nb is 1.3%;
The 3rd step, the melting of Zr (Nb) prealloy ingot
At first Zr, Nb metal charge are mixed; place it in the water jacketed copper crucible of arc-melting furnace; adopting the non-consumable arc melting method is melting Zr (Nb) alloy under the argon shield of 0.04MPa at air pressure; the melting voltage that is adopted is 16 volts; power is 5 kilowatts; smelting temperature is controlled at 2800K, measures melt temperature by infrared thermometer, and the current density during melting is 150A/cm
2, continue the molten alloy melt to the temperature back and cut off the power supply after 10 seconds, allow alloy be cooled to room temperature with copper crucible, then with its upset, place again in the water jacketed copper crucible, carry out the melting second time, so melt back is 4 times, obtains the uniform Zr of composition (Nb) prealloy ingot;
The 4th step, the melting of Cu-Zr-Nb alloy pig
The Cu raw material is mixed with Zr (Nb) prealloy ingot, adopt the non-consumable arc melting method to carry out melting under the protection of argon gas, the arc-melting furnace internal gas pressure is 0.04MPa, and smelting temperature is 2800K, and current density is 150A/cm
2, measure melt temperature by infrared thermometer, after 10 seconds of the lasting melting in temperature back, cut off the power supply, allow alloy be cooled to room temperature,, place in the water jacketed copper crucible again then with its upset with copper crucible, carry out the melting second time, so melt back is 3 times, obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 5th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, and with non-consumable arc melting method molten alloy, the arc-melting furnace internal gas pressure is 0.04MPa under argon shield, and smelting temperature is 2800K, and current density is 150A/cm
2Measure melt temperature by infrared thermometer, cut off the power supply after continuing 10 seconds of melting to temperature back, open the negative pressure absorbing and casting device simultaneously, the air pressure and the draught head in the arc-melting furnace of negative pressure bomb are 0.02MPa when inhaling casting, allow alloy melt charge into fast in the columniform copper mold die cavity, be cooled to room temperature, obtain the alloy bar that diameter is 3mm;
The 6th step, structure and performance test
(Cu K α radiation, its wavelength X=0.15406nm) is analyzed Cu with X-ray diffractometer
46.4Zr
52.3Nb
1.3The phase structure of alloy bar, the diffractive features that presents typical amorphous structure of its X-ray diffraction spectrum shows that it is a non-crystaline amorphous metal, does not wherein contain the crystal phase.Measure the thermodynamical coordinate of this alloy with differential scanning calorimeter and differential thermal analyzer, obtained its second-order transition temperature T
gBe 710K, crystallization temperature T
xBe 742K, Cu is described
46.4Zr
52.3Nb
1.3Block amorphous alloy has higher thermostability.Simultaneously, its reduction glass transformation temperature T
g/ T
l(0.593) and parameter γ (0.389) show the very strong amorphous formation ability that has of this alloy, in fact it to have formed diameter be the non-crystal bar of 3mm.Further vickers microhardness test shows: Cu
46.4Zr
52.3Nb
1.3The microhardness of block amorphous alloy reaches 587, rule of thumb formula σ
y=3Hv, can estimate its yield strength is 1760MPa.
Embodiment two, Cu
45.2Zr
51.0Nb
3.8Block amorphous alloy preparation and performance test thereof
The first step, the selection of alloying constituent
The system of selection of alloying constituent is determined alloying constituent with the first step among the embodiment one---Cu
45.2Zr
51.0Nb
3.8
Second step, the weighing of composition proportion
According to the alloying constituent of design, weighing purity in proportion is 99% high pure metal Zr, Nb and Cu raw material, and wherein, the amount of Cu is 45.2%, and the amount of Zr is 51.0%, and the amount of Nb is 3.8%;
The 3rd step, the melting of Zr (Nb) prealloy ingot
The melting method of Zr (Nb) prealloy ingot adopts the method in the 3rd step among the embodiment one to carry out.Its smelting temperature is 3000K, and current density is 160A/cm
2Ar pressure in the arc-melting furnace is 0.03MPa, after melt back 4 times, obtains the uniform Zr of composition (Nb) prealloy ingot;
The 4th step, the melting of Cu-Zr-Nb alloy pig
The fusion process of Cu-Zr-Nb alloy is with the method for embodiment one among the embodiment one in the 4th step.But its smelting temperature is 2700K, and current density is 140A/cm
2Ar pressure is 0.03MPa in the arc-melting furnace, after melt back 3 times, obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 5th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, and with non-consumable arc melting method molten alloy, the arc-melting furnace internal gas pressure is 0.03MPa under argon shield, and smelting temperature is 2700K, and current density is 140A/cm
2Measure melt temperature by infrared thermometer, cut off the power supply after continuing 10 seconds of melting to temperature back, open the negative pressure absorbing and casting device simultaneously, the air pressure and the draught head in the arc-melting furnace of negative pressure bomb are 0.015MPa when inhaling casting, allow alloy melt charge into fast in the columniform copper mold die cavity, be cooled to room temperature, obtain the alloy bar that diameter is 3mm;
The 6th step, structure and performance test
Structure and The performance test results show Cu
45.2Zr
51.0Nb
3.8Alloy bar is an amorphous structure, does not wherein contain any crystal phase.Its T
gWith T
xValue is respectively 717K and 747K; Its T
g/ T
lBe respectively 0.599 and 0.390 with the γ value.These show: at Cu-Zr-Nb is in the non-crystaline amorphous metal, and it is to have one of best heat alloy steady and the highest amorphous formation ability.
Embodiment three, Cu
39.7Zr
44.8Nb
15.5The block amorphous alloy preparation
The first step, the selection of alloying constituent
The system of selection of alloying constituent is determined alloying constituent with the first step among the embodiment one---Cu
39.7Zr
44.8Nb
15.5
Second step, the weighing of composition proportion
According to the alloying constituent of design, weighing purity in proportion is 99% high pure metal Zr, Nb and Cu raw material, and wherein, the amount of Cu is 39.7%, and the amount of Zr is 44.8%, and the amount of Nb is 15.5%;
The 3rd step, the melting of Zr (Nb) prealloy ingot
The melting method of Zr (Nb) prealloy ingot adopts the method in the 3rd step among the embodiment one to carry out.Its smelting temperature is 3200K, and current density is 170A/cm
2Ar pressure in the arc-melting furnace is 0.02MPa, after melt back 4 times, obtains the uniform Zr of composition (Nb) prealloy ingot;
The 4th step, the melting of Cu-Zr-Nb alloy pig
The fusion process of Cu-Zr-Nb alloy is with the method for embodiment one among the embodiment one in the 4th step.But its smelting temperature is 2000K, and current density is 120A/cm
2Ar pressure is 0.02MPa in the arc-melting furnace, after melt back 3 times, obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 5th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, and with non-consumable arc melting method molten alloy, the arc-melting furnace internal gas pressure is 0.02MPa under argon shield, and smelting temperature is 2000K, and current density is 120A/cm
2Measure melt temperature by infrared thermometer, cut off the power supply after continuing 10 seconds of melting to temperature back, open the negative pressure absorbing and casting device simultaneously, the air pressure and the draught head in the arc-melting furnace of negative pressure bomb are 0.01MPa when inhaling casting, allow alloy melt charge into fast in the columniform copper mold die cavity, be cooled to room temperature, obtain the alloy bar that diameter is 3mm;
The 6th step, structured testing
The X-ray diffraction result shows Cu
39.7Zr
44.8Nb
15.5Alloy bar is an amorphous structure, is block amorphous alloy.
Embodiment four, Cu
44.1Zr
49.8Nb
6.1The block amorphous alloy preparation
The first step, the selection of alloying constituent
The system of selection of alloying constituent is determined alloying constituent with the first step among the embodiment one---Cu
53.4Zr
41.9Nb
5.7
Second step, the weighing of composition proportion
According to the alloying constituent of design, weighing purity in proportion is 99% high pure metal Zr, Nb and Cu raw material, and wherein, the amount of Cu is 44.1%, and the amount of Zr is 49.8%, and the amount of Nb is 6.1%;
The 3rd step, the melting of Zr (b) prealloy ingot
The melting method of Zr (Nb) prealloy ingot adopts the method in the 3rd step among the embodiment one to carry out.Its smelting temperature is 2900K, and current density is 160A/cm
2Ar pressure in the arc-melting furnace is 0.03MPa, after melt back 4 times, obtains the uniform Zr of composition (Nb) prealloy ingot;
The 4th step, the melting of Cu-Zr-Nb alloy pig
The fusion process of Cu-Zr-Nb alloy is with the method for embodiment one among the embodiment one in the 4th step.But its smelting temperature is 2000K, and current density is 120A/cm
2Ar pressure is 0.03MPa in the arc-melting furnace, after melt back 3 times, obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 5th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, and with non-consumable arc melting method molten alloy, the arc-melting furnace internal gas pressure is 0.03MPa under argon shield, and smelting temperature is 2000K, and current density is 120A/cm
2Measure melt temperature by infrared thermometer, cut off the power supply after continuing 10 seconds of melting to temperature back, open the negative pressure absorbing and casting device simultaneously, the air pressure and the draught head in the arc-melting furnace of negative pressure bomb are 0.01MPa when inhaling casting, allow alloy melt charge into fast in the columniform copper mold die cavity, be cooled to room temperature, obtain the alloy bar that diameter is 3mm;
The 6th step, structured testing
The X-ray diffraction result shows Cu
44.1Zr
49.8Nb
6.1Alloy bar is an amorphous structure, is block amorphous alloy.
Embodiment five, Cu
42.2Zr
47.6Nb
10.2The block amorphous alloy preparation
The first step, the selection of alloying constituent
The system of selection of alloying constituent is determined alloying constituent with the first step among the embodiment one---Cu
42.2Zr
47.6Nb
10.2
Second step, the weighing of composition proportion
According to the alloying constituent of design, weighing purity in proportion is 99% high pure metal Zr, Nb and Cu raw material, and wherein, the amount of Cu is 42.2%, and the amount of Zr is 47.6%, and the amount of Nb is 10.2%;
The 3rd step, the melting of Zr (Nb) prealloy ingot
The melting method of Zr (Nb) prealloy ingot adopts the method in the 3rd step among the embodiment one to carry out.Its smelting temperature is 3100K, and current density is 170A/cm
2Ar pressure in the arc-melting furnace is 0.02MPa, after melt back 4 times, obtains the uniform Zr of composition (Nb) prealloy ingot;
The 4th step, the melting of Cu-Zr-Nb alloy pig
The fusion process of Cu-Zr-Nb alloy is with the method for embodiment one among the embodiment one in the 4th step.But its smelting temperature is 2300K, and current density is 130A/cm
2Ar pressure is 0.03MPa in the arc-melting furnace, after melt back 3 times, obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 5th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, and with non-consumable arc melting method molten alloy, the arc-melting furnace internal gas pressure is 0.03MPa under argon shield, and smelting temperature is 2300K, and current density is 130A/cm
2Measure melt temperature by infrared thermometer, cut off the power supply after continuing 10 seconds of melting to temperature back, open the negative pressure absorbing and casting device simultaneously, the air pressure and the draught head in the arc-melting furnace of negative pressure bomb are 0.015MPa when inhaling casting, allow alloy melt charge into fast in the columniform copper mold die cavity, be cooled to room temperature, obtain the alloy bar that diameter is 3mm;
The 6th step, structured testing
The X-ray diffraction result shows Cu
42.2Zr
47.6Nb
10.2Alloy bar is an amorphous structure, is block amorphous alloy.
The typical composition and the characteristic temperature measuring result of table 1:Cu-Zr-Nb block amorphous alloy.
| Composition(at％) | T g(K) | T x(K) | ΔT x(K) | T l(K) | T g/T l | γ |
| Cu 46.4Zr 52.3Nb 1.3 Cu 45.8Zr 51.7Nb 2.5 Cu 45.2Zr 51.0Nb 3.8 Cu 44.1Zr 49.8Nb 6.1 | 710 711 717 711 | 742 743 747 742 | 32 32 30 31 | 1197 1198 1196 1196 | 0.593 0.593 0.599 0.594 | 0.389 0.389 0.390 0.389 |
Room temperature density p, hardness Hv and the yield strength σ of table 2:Cu-Zr-Nb block amorphous alloy and other Cu base noncrystal alloy
yComparison
| Composition(at％) | ρ(g/cm 3) | Hv(kg/mm 2) | σ y(MPa) |
| Cu 46.4Zr 52.3Nb 1.3 Cu 45.8Zr 51.7Nb 2.5 Cu 45.2Zr 51.0Nb 3.8 Cu 54.3Zr 38.9Ti 6.8(with reference to composition) | 7.710 7.720 7.730 7.630 | 587 567 566 567 | 1761 1701 1698 1701 |
Claims (5)
1.Cu-Zr-Nb series bulk amorphous alloy comprises Cu element and Zr element, it is characterized in that:
(a). also include minor N b element;
(b) the composition general formula of the series bulk amorphous alloy of .Cu-Zr-Nb is: (Cu
xZr
1-x)
1-yNb
y, wherein, the span of x is: 40wt.%5x≤65wt.%, and the span of y is:
1wt.%≤y≤15wt.%, wt.% represents weight percent.
2. the processing method of the series bulk amorphous alloy of the preparation described Cu-Zr-Nb of claim 1 comprises composition proportion weighing, Heating temperature, fusion process and speed of cooling, it is characterized in that:
(a). proceed step by step is answered in melting, has comprised melting to Zr (Nb) prealloy ingot, to the melting of Cu-Zr-Nb alloy pig and the preparation of Cu-Zr-Nb block amorphous alloy;
(b). processing step is:
The first step is got the raw materials ready
Take by weighing the value of each constituent element by the weight percent of design mix, the purity requirement of Cu, Zr, Nb raw metal is 99%, and with Zr, Nb metal charge mixing for standby use;
Second step, the melting of Zr (Nb) prealloy ingot
The compound of Zr and Nb metal is placed in the water jacketed copper crucible of arc-melting furnace; adopt the non-consumable arc melting method under the protection of argon gas, to carry out melting; temperature is 2800K～3200K; measure melt temperature by infrared thermometer; and control smelting temperature by adjusting current density, the span of control of current density is: 150A/cm
2～170A/cm
2, cut off the power supply after continuing 10 seconds of melting to temperature back, allow alloy be cooled to room temperature with copper crucible, then with its upset, place again in the water jacketed copper crucible, carry out melting second time, melt back like this repeatedly obtains the uniform Zr of composition (Nb) prealloy ingot;
The 3rd step, the melting of Cu-Zr-Nb alloy pig
The Cu raw material is mixed with Zr (Nb) prealloy ingot; adopt the non-consumable arc melting method under the protection of argon gas, to carry out melting; smelting temperature is 2000K～2800K; measure melt temperature by infrared thermometer; and control smelting temperature by adjusting current density, the span of control of current density is: 120A/cm
2～150A/cm
2, cut off the power supply after continuing 10 seconds of melting to temperature back, allow alloy be cooled to room temperature with copper crucible, then with its upset, place again in the water jacketed copper crucible, carry out melting second time, melt back like this repeatedly obtains the uniform Cu-Zr-Nb alloy pig of composition;
The 4th step, the preparation of Cu-Zr-Nb block amorphous alloy
The Cu-Zr-Nb alloy pig is placed in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, under argon shield,, measure melt temperature by infrared thermometer, and pass through 120A/cm with non-consumable arc melting method molten alloy
2～150A/cm
2Current density control melt temperature, smelting temperature is 2000K～2800K, cuts off the power supply after continuing 10 seconds of melting to temperature back, opens the negative pressure absorbing and casting device simultaneously, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains block amorphous alloy.
3. according to the processing method of the series bulk amorphous alloy of the claim 2 preparation described Cu-Zr-Nb of claim 1, it is characterized in that the ar pressure in the arc-melting furnace is 0.02MPa～0.04MPa.
4. according to the processing method of the series bulk amorphous alloy of the claim 2 preparation described Cu-Zr-Nb of claim 1, it is characterized in that the draught head when the copper mold negative pressure is inhaled casting is 0.01MPa～0.02MPa.
5. according to the processing method of the series bulk amorphous alloy of the claim 2 preparation described Cu-Zr-Nb of claim 1, it is characterized in that obtaining diameter by copper mold negative pressure suction casting method is the block amorphous alloy rod of 3mm, its critical cooling velocity that forms amorphous is 10
3～10
2K/s.
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| CN103334066A (en) * | 2013-06-13 | 2013-10-02 | 上海理工大学 | Cu-Zr-Nd bulk amorphous alloy and preparation method thereof |
| CN103589882B (en) * | 2013-12-02 | 2016-01-20 | 东南大学 | A kind of block height entropy metallic glass and preparation method thereof |
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