CN100560774C - The Sm-Al-Co system Sm base ternary block amorphous alloy - Google Patents
The Sm-Al-Co system Sm base ternary block amorphous alloy Download PDFInfo
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Abstract
Sm-Al-Co system Sm base ternary block amorphous alloy in the field of new, feature: its composition range is Sm
x(Al
50-yCo
50+y)
100-x(x=50～58 at.%, y=-10～+ 7at.%); It is Sm that best amorphous forms composition
50Al
25Co
25The method for preparing above-mentioned alloy is: the copper mold negative pressure of the inspection of non-consumable arc melting, the rare-earth Sm volatile quantity of batching, alloy pig and compensation, block amorphous alloy is inhaled casting, the Ar Pressure 0.06～0.08MPa of Cai Yonging wherein, current density range 120～140A/cm
2, negative pressure is inhaled casting draught head 0.04 ± 0.005MPa, obtains the block amorphous alloy that diameter is 3mm.Advantage is: overcome the base block amorphous constituent element of Sm and optimize complexity more, composition is chosen random deficiency, has developed new Sm-Al-Co system Sm base ternary block amorphous alloy system, and has determined optimal components; Help the above Sm base block amorphous alloy of development quaternary on this three metamembers basis; Inspection of Sm volatile quantity and additional method have been reduced the composition deviation.
Description
Technical field
The present invention relates to a series of Sm-Al-Co block amorphous alloys, belong to field of new with 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 and functional materials.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, the U.S. has been used for the Zr base block amorphous alloy multiple fields such as golf club, medicine equipment, armor-piercing head, satellite component, and the Samsung of Korea S is developing the mobile phone and the MP3 shell of Zr base noncrystal alloy.
The rare earth metal base block amorphous alloy is the very fast class non-crystaline amorphous metals of latest developments.Because rare earth element often has specific physical chemical property such as special magnetic, optics, these have the rare earth metal base block amorphous alloy of good physical and chemical performance to pay much attention to development abroad.It is the rare earth block amorphous alloy that Japan has developed La the earliest, and Nd base, Pr base rare earth block amorphous alloy with good magnetic performance; Chinese Academy of Sciences's physics then developed multiple rare earth based block amorphous alloys such as Ce base with own intellecture property, Pr base, Er base in succession.Compare with these rare earth based bulk amorphous alloy, the market outlook slower development also arranged though rare-earth Sm is base block amorphous.On the one hand, be to use maximum s-generation rare earth permanent-magnetic materials at present because Sm-Co is an alloy, market scale is huge, so people are always at research New type of S m base functional magnetic material.On the other hand, because the amorphous formation ability understanding to Sm base alloy is not clear, so exploitation Sm base block amorphous alloy is made slow progress, the at present known system that can prepare large-sized Sm base block amorphous alloy all is the above alloy system of quaternary seldom.Therefore, at present known first kind of Sm is base block amorphous is five yuan alloy, and composition is Sm
60Fe
10Al
10Co
15Cu
5(reference: G.J.Fan, W.Loser, S.Roth and J.Eckert, Acta Materialia, 48 (2000) 3823) have become the typical composition of Sm base block amorphous alloy.The method of its employing die casting has obtained the block amorphous alloy of diameter 3mm.This alloy adopts Cu and Co to go part substitute for Al and Fe to obtain on Sm-Fe-Al alloy basis, and Sm-Fe-Al alloy itself can not form block amorphous alloy.The shortcoming of this quinary alloy is: 1. the constituent element multicomponent is optimized complexity, causes being difficult in the performance that improves alloy on this composition basis by optimizing components, and how constituent element has also improved cost of alloy simultaneously; 2. for the composition of determining block amorphous alloy need carry out a large amount of tests, this certainly exists certain subjectivity and randomness; 3. owing to this easy oxidization burning loss and the volatilization when melting of this rare earth metal of Sm, make alloying constituent depart from amorphous component easily, the Composition Control difficulty, these all make development Sm base block amorphous alloy become quite difficult.
From existing research, block amorphous alloy all is a multicomponent alloy, and composition is the key factor of the alloy amorphous formation ability of influence, the selection of composition and control most important.In specific amorphous architectonical, have that the alloy of strong amorphous formation ability has definite composition, if depart from this composition, the amorphous formation ability of alloy will greatly reduce.
Present situation at the Sm base block amorphous alloy, the present invention adopts " the electron density criterion that block amorphous alloy forms " design alloy, utilize the method for vacuum arc melting and copper mold, and take measures to control Sm oxidization burning loss and volatilization, develop and novel Sm base ternary block amorphous alloy.
Summary of the invention
The objective of the invention is to overcome that prior art exists: 1. become component selections in many group members system and optimize complicated difficulty; 2. rely on the empirical mode of experiment to seek the block amorphous alloy composition, be difficult to avoid subjectivity and randomness; 3. the Sm group member is in fusion process, volatile unmanageable deficiency.Provide with the open new Sm-Al-Co system Sm base ternary block amorphous alloy of electron density criterion, determine the formation scope of its block amorphous alloy and the composition of maximum amorphous formation ability, special proposition technical solution of the present invention.
Realize that thinking of the present invention is, the electron density criterion of utilizing block amorphous alloy to form is determined the amorphous component of Sm-Al-Co system; Come the alloyage raw material according to the proportioning of design mix then, need add during batching to compensate his volatilization when the melting into some Sm; Use the non-consumable arc melting method, molten alloy ingot under the argon gas atmosphere protection is to prevent the oxidation of Sm; When melting, also to be carried out to branch inspection, promptly utilize the volatile weight loss of balance measurement alloy pig, supply weightless Sm, with the monitoring alloying constituent; Utilize copper mold negative pressure suction casting method to prepare the block amorphous alloy rod at last, and confirm the composition of amorphous alloy component scope and maximum formation ability.
Sm-Al-Co system Sm base ternary block amorphous alloy proposed by the invention is characterized in that:
The Sm-Al-Co system Sm base ternary block amorphous alloy comprises Sm, Al and Co element, and its composition is Sm
x(Al
50Co
50)
100-xComponent lines, x=50～58at.% in the formula, at.% are atomic percent, or discrete one-tenth branch Sm
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8
The method for preparing the Sm-Al-Co system Sm base ternary block amorphous alloy comprises composition proportion weighing, melting, composition inspection and inhales casting that proceed step by step is answered in melting, the steps include:
The first step is got the raw materials ready
According to the atomic percent in the design mix, convert weight percent wt.% to, take by weighing each constituent element value, stand-by; Wherein, Sm will add the amount into 2%, the volatilization when being used for the compensator alloy melting; And its purity of raw metal of Sm, Al and Co element should be more than 99%;
Second step, the melting of Sm-Al-Co alloy pig
Above-mentioned three kinds of raw materials mixing is placed in the water jacketed copper crucible of non-consumable arc furnace, under the protection of argon gas, carries out melting, at first be evacuated to 10
-2Pa, charging into argon gas to air pressure then is 0.06～0.08MPa, the melting current density range is 120～140A/cm
2, after the fusing, continuing 10 seconds of melting again, outage allows alloy be cooled to room temperature with copper crucible, then with its upset, places again in the water jacketed copper crucible, carries out melting second time, and melt back like this at least 3 times obtains the uniform Sm-Al-Co alloy pig of composition;
In the 3rd step, Sm-Al-Co alloy pig composition is checked
With the quality of analytical balance weighing Sm-Al-Co alloy pig, this actual mass quality of raw material when getting the raw materials ready is compared, both differences are the volatilization quality of Sm element in the alloy; If Sm evaporable amount is less than in 2%, this alloy pig can carry out next step operation so; If Sm evaporable amount greater than 2%, needs to replenish the value of evaporable Sm element so, and repeatedly even by the method melting in second step again to guarantee the alloy pig composition;
The 4th step, the preparation of Sm-Al-Co block amorphous alloy
With the Sm-Al-Co alloy pig, place in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, under argon shield,, at first be evacuated to 10 with non-consumable arc melting method molten alloy
-2Pa, charging into argon gas to air pressure then is 0.06～0.08MPa, the melting current density range is 120～140A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains block amorphous alloy.
Of the present invention being further characterized in that: the alloying constituent that has maximum amorphous formation ability in the alloy of being applied for is Sm
50Al
25Co
25
The solution of the present invention is according to " the electron density criterion that block amorphous alloy forms ", phasor feature in conjunction with the Sm-Al-Co alloy system, determine electron density value in this alloy system and be 1.5 feature constant electron concentration line, determine the alloying constituent on this constant electron concentration line simultaneously, then on these composition bases, it is constant to fix two element proportionings, changes another element proportioning, thereby near the amorphous component scope the constant electron concentration line is determined and optimized.The main drawback of prior art has been avoided in this composition design concept, divide the randomness choose.Adopt non-consumable arc-melting furnace and copper mold negative pressure to inhale casting machine then, the method by the Composition Control that proposes in the thinking of the present invention prepares the Sm-Al-Co block amorphous alloy.With the structure and the thermodynamical coordinate of X-ray diffractometer, differential scanning calorimeter (TA Q100) assay determination alloy, determining the Sm-Al-Co that can form 3mm diameter amorphous bar with suction casting method is the Sm base block amorphous alloy, and its composition is Sm
x(Al
50Co
50)
100-xComponent lines (x=50～58at.%, at.% are atomic percent) become branch Sm with discrete
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8Also determine the composition that has maximum amorphous formation ability in these alloys simultaneously.
X-ray diffraction is the result show, when Sm-Al-Co is that the composition of alloy bar is when being positioned at outside the formation composition range of the block amorphous alloy that the present invention proposes, to occur a large amount of bright and sharp diffraction peaks in the X-ray diffraction spectrum of alloy, and show to have generated a large amount of crystal phases in the alloy; And when the composition of alloy bar was positioned at the composition range of the formation block amorphous alloy that the present invention proposes, its X-ray diffraction spectrum all presented typical non-crystalline state diffractive features, shows that they are block amorphous alloys.Finally, experiment is determined: the Sm-Al-Co that proposes in the present invention is in the composition range of Sm base block amorphous alloy, all can obtain the non-crystal bar of diameter 3mm by copper mold casting.Wherein, typical composition Sm
50Al
25Co
25, Sm
58Al
21Co
21, Sm
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8The amorphous quality of alloy is analyzed the DSC 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.
Glass transformation temperature T
gWith crystallization temperature 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; Both difference DELTA Tx (Δ T
x=T
g-T
x) having characterized the width of non-crystaline amorphous metal supercooling liquid phase region, the thermostability of the wide more then amorphous in this interval is also good more.The T of Sm-Al-Co system Sm base ternary block amorphous alloy
gAnd T
xValue shows that than higher they all have higher thermostability, and Sm
50Al
25Co
25Block amorphous alloy has maximum T
gAnd T
xValue shows to have optimal heat stability, and this alloy also has maximum Δ T simultaneously
x, show that it is at T
gThe ability that also has the strongest opposing crystallization more than the temperature.It is than known Sm
60Fe
10Al
10Co
15Cu
5Block amorphous alloy has higher T
gAnd T
x, promptly have better thermostability.
Reduction glass transformation temperature T
Rg=T
g/ T
lIt is the significant parameter that characterizes amorphous formation ability.The reduction glass transformation temperature of four block amorphous alloys is all bigger in the table 1, all greater than 0.6, promptly greater than the T that can effectively suppress the alloy forming core
RgThreshold value shows that these non-crystaline amorphous metals have very strong amorphous formation ability.The T of Sm-Al-Co system Sm base ternary block amorphous alloy
RgVery high, show that they have very strong amorphous formation ability.Similarly, characterize the parameter γ (γ=T of amorphous formation ability from another
x/ (T
g+ T
l)) value, show that also they have very strong amorphous formation ability.Wherein, Sm
50Al
25Co
25Block amorphous alloy has maximum T
RgWith the γ value, be the alloy of maximum amorphous formation ability.Its T
RgWith γ also than known Sm
60Fe
10Al
10Co
15Cu
5Bigger, have bigger amorphous formation ability.
By above-mentioned experimental analysis, can draw following result: utilize non-consumable arc melting and copper mold negative pressure to inhale the casting preparation method, and the method for the control alloying constituent that proposes of the present invention, the Sm-Al-Co that the present invention proposes is that can to form diameter in the Sm base alloy be the 3mm block amorphous alloy, its composition is Sm
x(Al
50Co
50)
100-x(x=50～58at.%) becomes branch Sm with discrete to component lines
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8The composition of maximum amorphous formation ability is Sm in these alloys
50Al
25Co
25
Need to prove that whole melting and suction casting process must be extracted into high back of the body end vacuum (10
-2Pa) charge into after under the argon shield and carry out,, also prevent to make technic metal composition off-design composition because of oxidation to avoid oxidation; Melting the used current density range of alloy involved in the present invention is 120～140A/cm
2Because excessive current density will cause a large amount of scaling loss volatilizations of Sm element, too small current density then will be removed the higher Co of fusing point in the melted alloy the long time, make a large amount of scaling loss of Sm element volatilize, so for Co content height and the low alloy of Sm content high current density, otherwise then use low current density; Must check and compensate alloy volatilization during melting, guarantee that the technic metal composition is near design mix.
Advantage of the present invention is: 1. overcome in the prior art the base block amorphous constituent element of Sm and optimized complexity more, composition is chosen the deficiency that has random and subjectivity, develop new Sm-Al-Co system Sm base ternary block amorphous alloy system, and determined block amorphous alloy composition range in this system; 2. because the alloy constituent element is simple and determined the block amorphous alloy composition of maximum formation ability, help on this composition basis, further developing the Sm base block amorphous alloy more than the quaternary; 3. taked volatile quantity inspection and additional method owing in the melting, so reduced the composition deviation.
The subordinate list explanation
Table 1 is the typical composition and the characteristic temperature measuring result of Sm-Al-Co system Sm base ternary block amorphous alloy
First row have provided the composition of exemplary alloy in the table, T in first row
gThe expression second-order transition temperature, T
xCrystallization temperature, supercooling liquid phase region Δ T
x, T
lThe liquidus point temperature, T
g/ T
lThe reduction glass transformation temperature, parameter γ (γ=T
x/ (T
g+ T
l)).The result shows that this system 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 Sm
50Al
25Co
25
For the typical composition of the block amorphous alloy that provides in the table, the component lines Sm that provides among they and the present invention
x(Al
50Co
50)
100-x(x=50～58at.%) relation of general formula is as follows: with the typical composition Sm that provides in the table
50Al
25Co
25And Sm
58Al
21Co
21For example describes.1) when x=50at.%, in the substitution empirical formula, the content that obtains Sm is 50at.%, and the content of Al is 50* (100-50)/100=25at.%, Co content be 50* (100-50)/100=25at.%, this alloying constituent is Sm
50Al
25Co
252) when x=58at.%, in the substitution component lines general formula, the content that obtains Sm is 58at.%, and the content of Al is 50* (100-58)/100=21at.%, Co content be 50* (100-58)/100=21at.%, this alloying constituent is Sm
58Al
21Co
21Other three typical composition points also can form 3mm diameter non-crystaline amorphous metal rod in the table in addition, and composition is respectively Sm
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8, they all are the one-tenth branches that obtains by test.
Description of drawings
Fig. 1 is a Sm-Al-Co system Sm base ternary block amorphous alloy variation diagram
Choosing with true of Sm-Al-Co system Sm base ternary block amorphous alloy composition is described by reference to the accompanying drawings Fixed. At first in the ternary component-part diagram, set up the constant electron concentration line. Usually, be easy to form bulk amorphous alloy Alloying component just be distributed on the constant electron concentration line, and restricted by the sub-concentration line of power transformation criterion. Because The electron concentration value of knowing the Sm metal is 1.5, and in the known Al-Co subgroup unit system typical electronics is arranged Phase Al50Co
50, its electron concentration value also is 1.5, connects so Sm and Al in Sm-Al-Co ternary component-part diagram50Co
50, constructing the constant electron concentration line, its composition can be expressed as Smx(Al
50Co
50)
100-x(formula In x=0～100at.%), i.e. fine line among Fig. 1. Secondly, in the ternary component-part diagram, set up power transformation Concentration line, the sub-concentration line of power transformation have shown that ternary block amorphous alloy is related with the composition of its subgroup unit alloy. Adopt respectively eutectic point Sm64Co
36With Sm75Al
25Make up the sub-concentration line of power transformation, connect with them Three component A l and Co just obtain two the sub-concentration lines of power transformation, i.e. dotted line among Fig. 1 and chain-dotted lines. Like this, Constant electron concentration line and two sub-concentration lines of power transformation intersect can obtain two intersection points, and the intersection point composition is Sm47Al
26.5Co
26.5And Sm60Al
20Co
20 In the intersection point scope and along the constant electron concentration line, designed Alloy, its composition can be expressed as Smx(Al
50Co
50)
100-x(x=47 in the formula～60at.%). Again, exist On these composition bases, it is constant to fix two element proportionings, changes another element proportioning, the electronics such as research Near the concentration line possible amorphous component scope. At last, determining Sm-Al-Co according to experiment is Sm The composition range of base ternary block amorphous alloy reality and the composition of maximum amorphous formation ability. Sm-Al-Co The system Sm base ternary block amorphous alloy composition is Smx(Al
50Co
50)
100-xComponent lines, x=50～58at.% becomes branch Sm with discrete54Al
19.8Co
26.2、Sm
54Al
27.6Co
18.4、Sm
52Al
26.2Co
21.8, in Fig. 1 Be expressed as separated time with the line segment between 1 and 2, be labeled as 3,4 and 5 triangle form point represent from The alloying component point that looses. In addition, to be labeled as 1,2,3,4 and 5 triangle form point be five typical cases to Fig. 1 Composition Sm50Al
25Co
25、Sm
58Al
21Co
21、Sm
54Al
19.8Co
26.2、Sm
54Al
27.6Co
18.4、
Sm
52Al
26.2Co
21.8。
Embodiment
Below in conjunction with subordinate list, describe the embodiment of Sm-Al-Co system Sm base ternary block amorphous alloy in detail, existing with composition Sm
50Al
25Co
25, Sm
58Al
21Co
21, Sm
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8Be example, the preparation process of Sm-Al-Co system Sm base ternary block amorphous alloy is described.And, the thermodynamics characteristics of this system bulk amorphous alloy are described in conjunction with subordinate list.
Embodiment one, Sm
50Al
25Co
25Block amorphous alloy preparation and performance test thereof
The first step, the weighing of composition proportion
According to the atomic percent in the design mix, convert weight percent wt.% to, weighing purity in proportion is 99.9% pure metal Sm, Al, Co raw material, and is stand-by; Volatilization when adding to be used for the compensator alloy melting in the weighing in advance into 2% Sm;
Second step, Sm
50Al
25Co
25The melting of ternary alloy ingot
With the compound of Al, Co and rare earth metal Sm, be placed in the water jacketed copper crucible of non-consumable arc-melting furnace, under the protection of argon gas, carry out melting, at first be evacuated to 10
-2Pa, charging into argon gas to air pressure then is 0.06MPa, the melting current density range is 140A/cm
2, after the fusing, continuing 10 seconds of melting again, outage allows alloy be cooled to room temperature with copper crucible, then with its upset, places again in the water jacketed copper crucible, carries out melting second time, and melt back like this 3 times obtains the uniform ternary alloy ingot of composition;
The 3rd step, Sm
50Al
25Co
25Ternary alloy ingot composition is checked
With the quality of balance measurement alloy pig, the precision of balance is ten thousand/gram; The quality of raw material when relatively this alloy pig quality and the first step are prepared burden, both differences are the volatilization quality of Sm element in the alloy; The alloy pig quality has reduced by 0.03 gram, be that Sm evaporable amount is 1.5% after the conversion, the evaporable amount is less than 2%, this alloy pig can carry out next step and inhale foundry work preface (having added the volatilization when 2%Sm is used to compensate melting when preparing burden owing to the first step in advance, so actual Sm content is about 50.5% in the alloy pig);
The 4th step, Sm
50Al
25Co
25The block amorphous alloy preparation
With Sm
50Al
25Co
25Alloy pig places in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, with non-consumable arc melting method molten alloy, at first is evacuated to 10 under argon shield
-2Pa, charging into argon gas to air pressure then is 0.06MPa, the used current density of melting is 140A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm;
The 5th step, structure and performance test
(Cu K α radiation, its wavelength X=0.15406nm) is analyzed Sm with X-ray diffractometer
50Al
25Co
25The 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, obtained its second-order transition temperature T
gBe 579K, crystallization temperature T
xBe 640K, Sm is described
50Al
25Co
25Block amorphous alloy has higher thermostability; Simultaneously, its reduction glass transformation temperature T
g/ T
l(0.648) and parameter γ (0.435) show the very strong amorphous formation ability that has of this alloy; Compare Sm with other non-crystaline amorphous metal in this system (sample all makes with under the similarity condition)
50Al
25Co
25Non-crystaline amorphous metal has high relatively T
g, T
x, T
g/ T
lWith the γ value, it is that amorphous best in the Sm-Al-Co system forms composition.
Embodiment two, Sm
58Al
21Co
21Block amorphous alloy preparation and performance test thereof
The first step, the weighing of composition proportion
According to the atomic percent in the design mix, convert weight percent wt.% to, weighing purity in proportion is 99.9% pure metal Sm, Al, Co raw material, and is stand-by; Add to be used for compensating its volatilization in the weighing in advance into 2% Sm;
Second step, Sm
58Al
21Co
21The melting of ternary alloy ingot
The melting method of alloy pig adopts the method in second step among the embodiment one to carry out; Vacuumize is 10
-2Pa, charging into ar pressure is 0.08MPa, the used current density of melting is 120A/cm
2, melt back 3 times obtains the uniform ternary alloy ingot of composition;
The 3rd step, Sm
58Al
21Co
21Ternary alloy ingot composition is checked
The inspection method of alloy pig volatilization quality adopts the method in the 3rd step among the embodiment one to carry out, and is slightly concrete; The quality of alloy pig has been lacked 0.068 gram, and promptly Sm has volatilized 3.4%, and volatile quantity needs to add Sm and controls alloying constituent greater than 2%; Because the alloy pig melting has been carried out 3 times, so Sm volatilization 0.0227 gram during each on average melting is the quality of the Sm that replenishes=0.068 gram-0.04 gram+0.0227 * 2=0.0734 gram so;
The 4th step, Sm
58Al
21Co
21The melting of ternary alloy ingot
Alloy pig is mixed with the Sm that replenishes,, obtain the uniform ternary alloy ingot of composition, specifically omit with the melting 2 times again of the method in the step of second among the embodiment one; The parameter that adopts is for vacuumizing 10
-2Pa charges into ar pressure 0.08MPa, the used current density 120A/cm of melting
2
The 5th step, Sm
58Al
21Co
21The block amorphous alloy preparation
With Sm
58Al
21Co
21Alloy pig places in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, with non-consumable arc melting method molten alloy, at first is evacuated to 1o under argon shield
-2Pa, charging into argon gas to air pressure then is 0.07MPa, the used current density of melting is 120A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm;
The 6th step, structure and performance test
(Cu K α radiation, its wavelength X=0.15406nm) is analyzed Sm with X-ray diffractometer
58Al
21Co
21The phase structure of alloy bar, the result shows Sm
52Al
24Co
24Alloy bar is an amorphous structure, does not wherein contain any crystal phase; The thermodynamical coordinate of this alloy, its T have been measured with differential scanning calorimeter
gWith T
xValue is respectively 554K and 585K; Its T
g/ T
lBe respectively 0.6193 and 0.404 with the γ value; The result shows, is in the non-crystaline amorphous metal at Sm-Al-Co, and it is one of alloy that has high thermostability and high amorphous formation ability.
Embodiment three, Sm
54Al
19.8Co
26.2The block amorphous alloy preparation
The first step, the weighing of composition proportion
According to the atomic percent in the design mix, convert weight percent wt.% to, weighing purity in proportion is 99.9% pure metal Sm, Al, Co raw material, and is stand-by; Add to be used for compensating its volatilization in the weighing in advance into 2% Sm;
Second step, Sm
54Al
19.8Co
26.2The melting of ternary alloy ingot
The melting method of alloy pig adopts the method in second step among the embodiment one to carry out; Vacuumize is 10
-2Pa, charging into ar pressure is 0.07MPa, the used current density of melting is 130A/cm
2, melt back 3 times obtains the uniform ternary alloy ingot of composition;
The 3rd step, Sm
54Al
19.8Co
26.2Ternary alloy ingot composition is checked
The inspection method of alloy pig volatilization quality adopts the method in the 3rd step among the embodiment one to carry out, and is slightly concrete; The quality of alloy pig has been lacked 0.0522 gram, and promptly Sm has volatilized 2.6%, and volatile quantity needs to add Sm and controls alloying constituent greater than 2%; Because the alloy pig melting has been carried out 3 times, so Sm volatilization 0.0174 gram during each on average melting is the quality of the Sm that replenishes=0.0522 gram-0.04 gram+0.0174 * 2=0.047 gram so;
The 4th step, Sm
54Al
19.8Co
26.2The melting of ternary alloy ingot
Alloy pig is mixed with the Sm that replenishes,, obtain the uniform ternary alloy ingot of composition, specifically omit with the melting 2 times again of the method in the step of second among the embodiment one; The parameter that adopts is for vacuumizing 10
-2Pa charges into ar pressure 0.08MPa, the used current density 130A/cm of melting
2
The 5th step, Sm
54Al
19.8Co
26.2The block amorphous alloy preparation
With Sm
54Al
19.8Co
26.2Alloy pig places in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, with non-consumable arc melting method molten alloy, at first is evacuated to 10 under argon shield
-2Pa, charging into argon gas to air pressure then is 0.08MPa, the used current density of melting is 130A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm;
The 6th step, structure and performance test
(Cu K α radiation, its wavelength X=0.15406nm) is analyzed Sm with X-ray diffractometer
54Al
19.8Co
26.2The phase structure of alloy bar, the result shows Sm
54Al
19.8Co
26.2Alloy bar is an amorphous structure, does not wherein contain any crystal phase; The thermodynamical coordinate of this alloy, its T have been measured with differential scanning calorimeter
gWith T
xValue is respectively 535K and 555K; Its T
g/ T
lBe respectively 0.607 and 0.392 with the γ value; The result shows, is in the non-crystaline amorphous metal at Sm-Al-Co, and it is one of alloy that has high thermostability and high amorphous formation ability.
Embodiment four, Sm
54Al
27.6Co
18.4The block amorphous alloy preparation
The first step, the weighing of composition proportion
According to the atomic percent in the design mix, convert weight percent wt.% to, weighing purity in proportion is 99.9% pure metal Sm, Al, Co raw material, and is stand-by; Add to be used for compensating its volatilization in the weighing in advance into 2% Sm;
Second step, Sm
54Al
27.6Co
18.4The melting of ternary alloy ingot
The melting method of alloy pig adopts the method in second step among the embodiment one to carry out; Vacuumize is 10
-2Pa charges into ar pressure for o.08MPa, and the used current density of melting is 130A/cm
2, melt back 3 times obtains the uniform ternary alloy ingot of composition;
The 3rd step, Sm
54Al
27.6Co
18.4Ternary alloy ingot composition is checked
The inspection method of alloy pig volatilization quality adopts the method in the 3rd step among the embodiment one to carry out, and is slightly concrete; The quality of alloy pig has been lacked 0.039 gram, and promptly Sm has volatilized 1.95%, and the evaporable amount is less than 2%, and this alloy pig can carry out next step and inhale the foundry work preface;
The 4th step, Sm
54Al
27.6Co
18.4The block amorphous alloy preparation
With Sm
54Al
27.6Co
18.4Alloy pig places in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, with non-consumable arc melting method molten alloy, at first is evacuated to 10 under argon shield
-2Pa, charging into argon gas to air pressure then is 0.07MPa, the used current density of melting is 130A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm.
The 5th step, structure and performance test
(Cu K α radiation, its wavelength X=0.15406nm) is analyzed Sm with X-ray diffractometer
54Al
27.6Co
18.4The phase structure of alloy bar, the result shows Sm
54Al
27.6Co
18.4Alloy bar is an amorphous structure, does not wherein contain any crystal phase; The thermodynamical coordinate of this alloy, its T have been measured with differential scanning calorimeter
gWith T
xValue is respectively 571K and 610K; Its T
g/ T
lBe respectively 0.618 and 0.408 with the γ value; The result shows, is in the non-crystaline amorphous metal at Sm-Al-Co, and it is one of alloy that has high thermostability and high amorphous formation ability.
Embodiment five, Sm
52Al
26.2Co
21.8The block amorphous alloy preparation
The first step, the weighing of composition proportion
According to the atomic percent in the design mix, convert weight percent wt.% to, weighing purity in proportion is 99.9% pure metal Sm, Al, Co raw material, and is stand-by; Add to be used for compensating its volatilization in the weighing in advance into 2% Sm;
Second step, Sm
52Al
26.2Co
21.8The melting of ternary alloy ingot
The melting method of alloy pig adopts the method in second step among the embodiment one to carry out; Vacuumize is 10
-2Pa, charging into ar pressure is 0.06MPa, the used current density of melting is 130A/cm
2, melt back 3 times obtains the uniform ternary alloy ingot of composition;
The 3rd step, Sm
52Al
26.2Co
21.8Ternary alloy ingot composition is checked
The inspection method of alloy pig volatilization quality adopts the method in the 3rd step among the embodiment one to carry out, and is slightly concrete; The quality of alloy pig has been lacked 0.038 gram, and promptly Sm has volatilized 1.9%, and the evaporable amount is less than 2%, and this alloy pig can carry out next step and inhale the foundry work preface;
The 4th step, Sm
52Al
26.2Co
21.8The block amorphous alloy preparation
With Sm
52Al
26.2Co
21.8Alloy pig places in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, with non-consumable arc melting method molten alloy, at first is evacuated to 10 under argon shield
-2Pa, charging into argon gas to air pressure then is 0.08MPa, the used current density of melting is 130A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains the block amorphous alloy that diameter is 3mm.
The 5th step, structure and performance test
(Cu K α radiation, its wavelength X=0.15406nm) is analyzed Sm with X-ray diffractometer
52Al
26.1Co
21.8The phase structure of alloy bar, the result shows Sm
52Al
26.2Co
21.8Alloy bar is an amorphous structure, does not wherein contain any crystal phase; The thermodynamical coordinate of this alloy, its T have been measured with differential scanning calorimeter
gWith T
xValue is respectively 574K and 636K; Its T
g/ T
lBe respectively 0.641 and 0.433 with the γ value; The result shows, is in the non-crystaline amorphous metal at Sm-Al-Co, and it is one of alloy that has high thermostability and high amorphous formation ability.
Table 1:Sm-Al-Co is the typical composition and the characteristic temperature measuring result of Sm base block amorphous alloy.
Claims (3)
1.Sm-Al-Co system Sm base ternary block amorphous alloy is characterized in that:
The Sm-Al-Co system Sm base ternary block amorphous alloy comprises Sm, Al and Co element, and its composition is Sm
x(Al
50Co
50)
100-xComponent lines, x=50～58at.% in the formula, at.% are atomic percent, or discrete one-tenth branch Sm
54Al
19.8Co
26.2, Sm
54Al
27.6Co
18.4, Sm
52Al
26.2Co
21.8
2. Sm-Al-Co system Sm base ternary block amorphous alloy according to claim 1 is characterized in that:
Sm
x(Al
50Co
50)
100-xComponent lines in have a maximum amorphous formation ability alloying constituent be Sm
50Al
25Co
25
3. the preparation method of claim 1 or 2 described non-crystaline amorphous metals, comprise get the raw materials ready, melting, composition detection and suction casting, melting should distribute and carry out, and the steps include:
The first step is got the raw materials ready
According to the atomic percent in the design mix, convert weight percent wt.% to, take by weighing each constituent element value, stand-by; Wherein, Sm will add the amount into 2%, the volatilization when being used for the compensator alloy melting; And its purity of raw metal of Sm, Al and Co element should be more than 99%;
Second step, the melting of Sm-Al-Co alloy pig
Three kinds of raw materials mixing are placed in the water jacketed copper crucible of non-consumable arc furnace, under the protection of argon gas, carry out melting, at first be evacuated to 10
-2Pa, charging into argon gas to air pressure then is 0.06～0.08MPa, the melting current density range is 120～140A/cm
2, after the fusing, in 10 seconds of lasting melting, outage allows alloy be cooled to room temperature with copper crucible, then with its upset, places again in the cold-crucible, carries out melting second time, and melt back like this at least 3 times obtains the uniform Sm-Al-Co alloy pig of composition;
In the 3rd step, Sm-Al-Co alloy pig composition is checked
With the quality of analytical balance weighing Sm-Al-Co alloy pig, this actual mass quality of raw material when getting the raw materials ready is compared, both differences are the volatilization quality of Sm element in the alloy; If Sm evaporable amount is less than in 2%, this alloy pig can carry out next step operation so; If Sm evaporable amount greater than 2%, needs to replenish the value of evaporable Sm element so, and melting guarantees that repeatedly the alloy pig composition is even again;
The 4th step, the preparation of Sm-Al-Co block amorphous alloy
With the Sm-Al-Co alloy pig, place in the water jacketed copper crucible that is connected with negative pressure suction casting equipment, under argon shield,, at first be evacuated to 10 with non-consumable arc melting method molten alloy
-2Pa, charging into argon gas to air pressure then is 0.06～0.08MPa, the melting current density range is 120～140A/cm
2, after the fusing, continuing 10 seconds of melting again, the negative pressure absorbing and casting device is opened in outage simultaneously, and draught head is 0.04 ± 0.005MPa, allows alloy melt charge in the cylindrical, copper model cavity, is cooled to room temperature, obtains block amorphous alloy.
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| EP0406770A1 (en) * | 1989-07-04 | 1991-01-09 | Ykk Corporation | Amorphous alloys superior in mechanical strength, corrosion resistance and formability |
| EP0503970A1 (en) * | 1991-03-14 | 1992-09-16 | Ykk Corporation | Magnetic refrigerant |
| JP3087338B2 (en) * | 1991-05-13 | 2000-09-11 | ミノルタ株式会社 | Copier with sorter |
| CN1924071A (en) * | 2005-08-31 | 2007-03-07 | 中国科学院物理研究所 | Samarium based amorphous alloy and preparation method thereof |
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| EP0406770A1 (en) * | 1989-07-04 | 1991-01-09 | Ykk Corporation | Amorphous alloys superior in mechanical strength, corrosion resistance and formability |
| EP0503970A1 (en) * | 1991-03-14 | 1992-09-16 | Ykk Corporation | Magnetic refrigerant |
| JP3087338B2 (en) * | 1991-05-13 | 2000-09-11 | ミノルタ株式会社 | Copier with sorter |
| CN1924071A (en) * | 2005-08-31 | 2007-03-07 | 中国科学院物理研究所 | Samarium based amorphous alloy and preparation method thereof |
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