CN109797352A - A kind of regulation method of amorphous alloy average atom cluster size - Google Patents
A kind of regulation method of amorphous alloy average atom cluster size Download PDFInfo
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Abstract
The invention discloses a kind of regulation methods of amorphous alloy average atom cluster size, the described method includes: the calculating step of amorphous alloy melt average atom cluster size: calculating the average atom cluster size of amorphous alloy melt under different temperatures, obtain the calculated result that average atom cluster size varies with temperature；Overheating Treatment step is carried out to alloy melt: the average atom cluster size needed according to calculated result selection, temperature corresponding with selected average atom cluster size is determined as to the Overheating Treatment temperature of alloy melt, the alloy melt is kept the temperature at a temperature of the Overheating Treatment, the alloy melt after obtaining Overheating Treatment；Quick coagulation step: the amorphous alloy melt after the Overheating Treatment is quickly solidified, non-crystalline solids alloy is obtained.The present invention has started the new concept and new method of amorphous alloy microstructure design and preparation, has the characteristics that easy, high-efficient, at low cost, engineering reliability is high.
Description
Technical field
The present invention relates to a kind of Metallic Functional Materials preparation technical field, in particular to a kind of amorphous alloy average atom
The regulation method of cluster size.
Background technique
The case where being divided into anions and canons from organic liquids such as water is different, is formed after alloy melting some very small size of
The atomic arrangement on elementide, elementide inside and surface is different from crystalline material, and with the variation of elementide size
And change.In determining alloy composition, size, geometry and the feature of elementide still with melt temperature not
Show notable difference together.Amorphous alloy remains the Structure of Atomic Clusters feature of melt, therefore elementide is to constitute
The basic unit of amorphous alloy electronic band structure.Crystalline material has the electronic band structure of periodic distribution, amorphous state
The electronic band structure of alloy is then locality, and the size of elementide determines the electronic band structure of each locality
Scale.But no matter crystalline material or amorphous alloy its macroscopic property both depend on their electronic band structure.It is different
The elementide of atom number, different sizes and different structure corresponds to different locality electronic band structure and size, so
Carrying out regulation to elementide size is to optimize an effective way of amorphous alloy macro property.
It is different from the Structure of Atomic Clusters of single type in pure simple substance metal bath, in alloy melt Structure of Atomic Clusters and
Size is not only closely related with alloy composition, also related with the temperature of melt.With the variation of melt temperature, amorphous alloy melt
Middle Structure of Atomic Clusters and size also occur accordingly change, therefore Structure of Atomic Clusters and size depend not only upon alloy at
Part, also there is apparent dependence to melt temperature.The Structure of Atomic Clusters of initial melt is bigger, with alloy melt temperature
The thermal vibration of the raising of degree, atom can be bigger, and the outermost atom of elementide can leave initial elementide, leads to atom
The reduction of cluster size.The atom left from elementide outermost layer enters melt, forms free atom, in same melt
Free atom also will form elementide.As atom leaves elementide, Structure of Atomic Clusters and size can also be adjusted,
To reduce the energy of elementide, increase the structural stability of elementide.Although the Structure of Atomic Clusters of amorphous alloy
It is in close relations with the macro property of size and amorphous alloy, it is the basis of realization amorphous alloy macro property, however due to closing
Structure of Atomic Clusters and size are complicated and multiplicity in golden melt, and are changed with melt temperature, and there is presently no experimental techniques
Method can directly measure the Structure of Atomic Clusters and size of non-crystalline solids alloy and melt, obtain Structure of Atomic Clusters and ruler
Very little information.
Summary of the invention
For the limitation of the prior art, the purpose of the present invention is to provide a kind of amorphous alloy average atom cluster rulers
Very little regulation method.The present invention can regulate and control amorphous alloy by changing the Overheating Treatment temperature of amorphous alloy melt
Average atom cluster size achievees the purpose that regulate and control amorphous alloy performance.
To achieve the goals above, the invention adopts the following technical scheme:
Since macro property has the dependence and sensibility of height to Structure of Atomic Clusters and size, non-crystalline solids are closed
Gold Structure of Atomic Clusters and size to its macro property have great influence, regulate and control amorphous alloy Structure of Atomic Clusters and
Size is one of the important channel of raising non-crystalline solids alloy property, but at present for regulating and controlling amorphous alloy elementide knot
Structure and size still lack effective technology method, it has also become non-crystalline solids alloy field is unsolved crucial and again
Want one of matter of science and technology.Effective Regulation amorphous alloy Structure of Atomic Clusters and the main reason for size it can not be a lack of tune
The method for controlling melt Structure of Atomic Clusters and size.Due to lacking the technical method of regulation melt Structure of Atomic Clusters and size,
Therefore required melt Structure of Atomic Clusters and size can not be solidified in amorphous alloy.Establish regulation amorphous alloy
The process of Structure of Atomic Clusters and size is both to meet important amorphous alloy ribbon investigation of materials and engineering production
Key technique, but also be research and develop high-performance non-crystalline solids alloy thin band material be badly in need of important technology.
Since the elementide in melt can not be measured by laboratory facilities, the binary of computer simulation alloy melt is utilized
Distribution function is undoubtedly a kind of effective means that melt Structure of Atomic Clusters is directly researched from atom distribution level, can be more complete
The Structure of Atomic Clusters information of melt is reflected in face, although this information is statistical.Although in initial amorphous alloy, such as iron
Iron atom, silicon atom and boron atom can form the atom collection of a large amount of different components and different types of structure in silicon B alloy melt
Group, but nonmetalloid is the key that melt composition non-crystalline solids alloy, because only that when metallic element surrounds nonmetallic member
When element forms elementide, melt could be rapidly solidificated into non-crystalline solids alloy, therefore using nonmetalloid as center shape
At iron-Si_n chuster, iron-boron and iron-silicon-boron atom cluster be only constitute non-crystalline solids alloy main atomic group
Cluster.In melt the combination of similar atom and foreign atom can by binary probability-distribution function g (r)=ρ (r) of alloy/
ρ0It obtains, ρ in formula0It is the average atomic density of material, when ρ (r) is indicated using any atom as center, the original on spherical surface at the distance r
The assembly average of sub- distribution probability, it is reflected in material away from the atom distribution at any atom different location.By g
(r) the neighbor relationships information of available foreign atom can although it cannot provide the specific spatial position of atom distribution
The assembly average for providing neighbour's atomic quantity and distance, be equivalent to by atom distribution three-dimensional information be compressed to it is one-dimensional.Melt
G (r) in some specific locations peak value can occur, illustrate the other atomicities for surrounding some specific atoms be distributed in and these
Distance corresponding to peak position, wherein the peak nearest apart from origin is the position of first neighbour's atom distribution, with distance
Increase, other peaks be followed successively by second, third, the 4th ... wait neighbours' atom be distributed position.It follows that neighbour peak
Quantity and the size of elementide are directly corresponding, and the quantity at neighbour peak, and the size for illustrating elementide is bigger, and neighbour peak
Intensity correspond to the neighbour layer atom distributed quantity.The area at each neighbour peak corresponds to the average atom number of neighbour layer
Amount, also referred to as average atom ligancy, can extrapolate possible elementide configuration and size by average atom ligancy.One
The area at a neighbour peak is bigger, and average atom ligancy is bigger in corresponding neighbour's layer, and the atomic quantity of neighbour layer is got over
It is more, it is also bigger to be formed by elementide size.It is closer at a distance from central atom for foreign atom, between atom
Interaction force is stronger, and the atomicity of distribution is more, and corresponding peak strength is bigger in g (r).With with central atom distance
Be continuously increased, the interaction force between foreign atom obviously weakens, and outer layer atom and central atom constitute the several of cluster structure
Rate declines rapidly, therefore neighbour peak remote with initial point distance in g (r) disappears, so that only existing limited amount in the g (r) of melt
Several neighbour peaks.Since the first neighbour peak is much stronger than other neighbour peaks, illustrate the cluster knot of the first neighbour layer atomic building
Structure occupies leading position in all elementides, so the cluster size of the first neighbour layer atomic building can be used as average original
Sub- cluster size.With the variation of melt temperature, the position at peak and intensity can all occur to change accordingly in g (r), illustrate melt
The structure snd size variation with temperature of elementide, wherein the variation of peak strength corresponds to the neighbour's atom for surrounding central atom
Quantity variation, the variation of this neighbour's atomic quantity illustrate the variation of elementide configuration, and elementide change of configuration is simultaneously
Correspond to the variation of elementide size.The quantity variation at neighbour peak then corresponds to increasing and decreasing for neighbour's atom number of plies.When close
The quantity at adjacent peak increases the increase or reduction for illustrating atom cluster size in melt at this time when perhaps reducing, so from g (r)
The variation of middle neighbour's peak number amount and intensity can accurately judge the situation of change of atom cluster size in melt.Due to
The cluster structure of one neighbour layer atomic building occupies leading position, by the Strength Changes at the first neighbour peak alternatively average atom
The foundation of cluster size.By the way that alloy melt is heated to temperature corresponding to selected elementide size, and quickly solidify
At the method for non-crystalline solids alloy, the regulation to amorphous alloy average atom cluster size is completed.
A kind of regulation method of amorphous alloy average atom cluster size, comprising:
The calculating step of amorphous alloy melt average atom cluster size: amorphous alloy melt is flat under calculating different temperatures
Equal elementide size obtains the calculated result that average atom cluster size varies with temperature；
Overheating Treatment step is carried out to alloy melt: the average atom cluster ruler needed according to calculated result selection
It is very little, temperature corresponding with selected average atom cluster size is determined as to the Overheating Treatment temperature of alloy melt, in institute
It states and the alloy melt is kept the temperature at a temperature of Overheating Treatment, the alloy melt after obtaining Overheating Treatment.
Quick coagulation step: the amorphous alloy melt after the Overheating Treatment is quickly solidified, and it is solid to obtain amorphous state
Body alloy.
In the calculating step of above-mentioned amorphous alloy melt average atom cluster size, as a preferred implementation manner,
The specific steps of the average atom cluster size of amorphous alloy melt under the calculating different temperatures are as follows: according to non-under different temperatures
The pair distribution of peritectic alloy melt calculates the area at the first neighbour peak, obtains the average atom ligancy of the first neighbour
With the average atom cluster size；Preferably, the pair distribution is by molecular dynamics or/and first principle molecule
Dynamics simulation method is calculated and is obtained；Preferably, the temperature range for calculating the average atom cluster size of alloy melt is 1300-
1800℃。
Alloy melt is carried out in Overheating Treatment step above-mentioned, is determining that alloy is molten as a preferred implementation manner,
Before keeping the temperature after the Overheating Treatment temperature of body and to the alloy melt, by the alloy melt with 5-15 DEG C/min
Rate be warming up to the Overheating Treatment temperature；Preferably, the soaking time is 1.5-3 hours, to make in alloy melt
Average atom cluster reach stable state identical with calculated result.Because the calculating step can only be inside melt in flat
It just can be carried out under weighing apparatus state, the result of acquired results certainly equilibrium state.Therefore heating rate is too fast, then is not easy to reach inside melt
To uniform equilibrium state；Heating rate is excessively slow, then will waste the unnecessary process time.Similarly, when the temperature change of melt
When to a new temperature, melt can not reach equilibrium state at once, it is necessary in this temperature regular hour, if protected
The warm time is too short, and the cluster structure of the undergone temperature in front has also been remained in melt.If soaking time is too long, will waste not
The necessary process time.
It is described as a preferred implementation manner, to be quickly solidified as by using high speed in above-mentioned quick coagulation step
Planar flow continuous casting technology is completed；Preferably, the high-speed plane stream caster technology are as follows: the amorphous alloy melt is passed through into nozzle
It is poured on high-speed rotating chill roll and carries out the quick solidification；It is highly preferred that the linear velocity of the cooling roller surface is
15-30 meter per second；Preferably, the non-crystalline solids alloy is thin ribbon shaped；Preferably, the thickness of the non-crystalline solids alloy
It is 18-32 microns；Preferably, the width of the non-crystalline solids alloy is 50-282 millimeters；Preferably, the non-crystalline solids
Before alloy is the amorphous alloy strip steel rolled stock of Fe base in amorphous alloy system, FeNi base, FeCo base and iron-base nanometer crystal alloy
Drive body；It is highly preferred that the non-crystalline solids alloy is Fe84Si10B6。
The present invention uses the phenomenon that Structure of Atomic Clusters is with Overheating Treatment temperature change in alloy melt, passes through simulation and calculates
Iron-silicon, iron-boron and the iron-silicon-boron atom cluster size formed centered on nonmetalloid is with Overheating Treatment temperature change
Feature establishes the corresponding relationship of alloy melt Overheating Treatment temperature Yu elementide size, selects to close using Overheating Treatment temperature
Suitable elementide size, and it is rapidly solidificated into non-crystalline solids alloy, realize non-crystalline solids alloy atom cluster ruler
Very little designability and controllable preparation.
The present invention has following good effect compared with prior art:
One, the regulation method of a kind of amorphous alloy average atom cluster size proposed by the present invention, has started amorphous state
The new concept and new method that alloy microstructure designs and prepares.
Two, the present invention be suitable for all amorphous ferromagnetic alloy strips, especially can alloy melt composition have compared with
Regulate and control the average atom cluster size of amorphous ferromagnetic alloy strip in the case where great fluctuation process.
Three, the present invention has be easy to implement, be high-efficient, is at low cost, controllability and repeatability are strong, engineering reliability is high etc.
Feature is suitable for the extensive use in Metallic Functional Materials preparation technical field.
Detailed description of the invention
Fig. 1 is that a kind of process blocks of the regulation method of amorphous alloy average atom cluster size proposed by the present invention are shown
It is intended to.
Fig. 2 is the Fe in the present invention at 1300 DEG C to 1800 DEG C84Si10B6The calculating knot of binary function in alloy melt
Fruit.
Fig. 3 is in the embodiment of the present invention 1 to Fe84Si10B6Alloy melt is in 1800 DEG C of progress Overheating Treatments and quickly solidification
The schematic diagram of the transmission electron microscope three-dimensionalreconstruction image of the amorphous alloy ribbon obtained afterwards.
Fig. 4 is the embodiment of the present invention 2 to Fe84Si10B6Alloy melt is after 1300 DEG C of progress Overheating Treatments and quickly solidification
The schematic diagram of the transmission electron microscope three-dimensionalreconstruction image of the amorphous alloy ribbon of acquisition.
Fig. 5 is the embodiment of the present invention 3 to Fe84Si10B6Alloy melt is after 1500 DEG C of progress Overheating Treatments and quickly solidification
The schematic diagram of the transmission electron microscope three-dimensionalreconstruction image of the amorphous alloy ribbon of acquisition.
Fig. 6 is the embodiment of the present invention 4 to Fe40Ni40P14B6Alloy melt is in 1300 DEG C of progress Overheating Treatments and quickly solidification
The schematic diagram of the transmission electron microscope three-dimensionalreconstruction image of the amorphous alloy ribbon obtained afterwards.
Specific embodiment
In order to make the content of the present invention more clearly understood, it below according to a specific embodiment of the invention and ties
Attached drawing is closed, the present invention is described in further detail.
In conjunction with Fig. 1 to Fig. 6, a kind of regulation method of amorphous alloy average atom cluster size proposed by the present invention, packet
Include following specific steps:
Step 1, calculate amorphous alloy melt in pair distribution with melt temperature variation: utilize molecular dynamics
Or/and first principle molecular dynamics simulation calculates amorphous alloy melt pair distribution with the change of melt temperature
Change, calculates the area at the first neighbour peak of different temperatures, and obtain corresponding first closely by the area at the first neighbour of gained peak
The average-size of adjacent average atom ligancy and the first neighbour layer atomic building cluster, obtains average atom cluster size with molten
The characteristics of temperature changes, and the alternatively foundation of average atom cluster size；Referring to fig. 2, as can be seen from Figure 2, with temperature
The peak height of the raising of degree, each neighbour peak is all substantially reduced, wherein the third and fourth neighbour peak fades away, illustrates elementide
Size reduces with the raising of melt overheat temperature.Elementide known to the position at the 4 neighbour peaks presented from g (r) curve
Maximum critical dimension is about 1 nanometer.What the abscissa at the first neighbour peak represented be on first neighbour's layer atom with surrounded
The distance of heart atom, what ordinate represented is atomic quantity over this distance, so the original with central atom different distance
The result of subnumber amount adduction is equal to the atomic quantity of all the first neighbour layers, i.e. the area at the first neighbour peak is equal to the first neighbour
The atomic quantity of layer.Since the area at the first neighbour peak is not usually an integer, and an independent elementide includes
Atomic quantity must be integer, this species diversity contains the cluster of various different atomic quantities, cluster in the first neighbour peak
Between have the case where shared first neighbour layer atom, so the average value of their the first neighbour layer atom is not integer, referred to as
Average atom ligancy.In addition to the of positive 4 face body, positive 8 face body, cube, regular dodecahedron and positive 20 face body this 5 kinds of regular polygons
One neighbour layer atom is identical outer at a distance from central atom, and for the elementide of other polyhedral structures, the first neighbour layer is former
Son is not identical at a distance from central atom, and far, what is had is closer for some distances.Under normal circumstances, the first neighbour layer is former
The average distance of son and central atom depends on the quantity of the first neighbour layer atom, and the atom of the first neighbour layer is more, with center
The distance of atom is remoter.In other words, average atom ligancy is bigger, and the size of elementide is bigger.Although the first neighbour peak
The available average atom ligancy of area, but due to the complexity of Structure of Atomic Clusters, identical average atom ligancy
Can be corresponding with a variety of elementides, have different sizes without isostructural elementide, such as close to circular cluster its
Size is less than the cluster of prolate, therefore does not have exact corresponding relationship between average atom ligancy and elementide size.
In this case, most stable of Structure of Atomic Clusters can only be made of average atom ligancy by calculating, and will be most stable
Elementide size as average-size.
Step 2, the Overheating Treatment temperature of amorphous alloy melt is determined according to pair distribution calculated result: first with
Average atom cluster size needed for the calculated result selection that alloy melt pair distribution changes with melt temperature, then by
Selected average atom cluster size determines corresponding melt temperature, the Overheating Treatment temperature as melt；
Step 3, amorphous alloy melt is heated in the temperature of setting: sets the heat treatment temperature of melt,
Amorphous alloy melt is heated to the heat treatment temperature of setting with the speed of 5-10 DEG C/min (such as 6,7,8,9 DEG C/min)
(the Overheating Treatment temperature i.e. in step 2) keeps the temperature 1.5-3 hours (such as 2,2.5,2.8 hours) later, flat in melt to make
Equal elementide size reaches stable state identical with calculated result；
Step 4, the amorphous alloy melt after heat treatment is quickly solidified and obtains non-crystalline solids alloy thin band: will heated
Treated, and iron silicon B alloy melt is continuously pouring on high-speed rotating rapid cooling copper roller by nozzle, the copper roller surface
Linear velocity is 15-30 meter per second (such as 16,18,20,22,23,25,26,28 meter per seconds), and the alloy melt after heat treatment is rapid
It is frozen into a thickness of the non-crystalline solids alloy thin band of 18-32 microns (such as 18,20,23,25,26,28,30,31 microns), realizes
Regulation to amorphous alloy ribbon average atom cluster size.
Embodiment 1
A kind of regulation method of amorphous alloy average atom cluster size, specific steps are as follows:
Step 1, Fe is calculated84Si10B6(index number in chemical formula is at%) amorphous alloy melt average atom cluster
Size with melt temperature variation: calculated first with molecular dynamics or/and first principle molecular dynamics simulation
Fe84Si10B6The pair distribution of alloy melt with melt temperature variation, then to the face at the first neighbour peak of different temperatures
Product is calculated, and the average atom ligancy elementide corresponding with the ligancy for obtaining corresponding first neighbour layer is averaged ruler
The calculated result that very little and average atom cluster size changes with melt temperature, in this, as selection average atom cluster size
Foundation；
Step 2, Fe is determined according to average atom cluster size84Si10B6The Overheating Treatment temperature of alloy melt: first with
Fe84Si10B6It is put down corresponding to 1800 DEG C of the calculated result selection that alloy melt average atom cluster size changes with melt temperature
Equal elementide size is about 0.5 nanometer, and by 1800 DEG C of Overheating Treatment temperature as melt；
Step 3, in the temperature of setting to Fe84Si10B6Alloy melt is heated: being set according to calculated result
Fe84Si10B6The Overheating Treatment temperature of melt, first by Fe84Si10B6Alloy melt is heated to setting with 10 DEG C/min of speed
1800 DEG C of Overheating Treatment temperature, 2 hours then are kept the temperature, to make Fe84Si10B6The average atom cluster size of melt reaches and counts
Calculate the identical stable state of result；
Step 4, by the Fe after heat treatment84Si10B6Alloy melt, which quickly solidifies, obtains non-crystalline solids alloy thin band: will
Fe after 1800 DEG C of Overheating Treatments84Si10B6Alloy melt is continuously pouring on high-speed rotating rapid cooling copper roller by nozzle,
The linear velocity of the copper roller surface is 25 meter per seconds, and alloy melt is by quick solidification at a thickness of 32 microns after 1800 DEG C of Overheating Treatments
Amorphous alloy ribbon, realize regulation to amorphous alloy ribbon average atom cluster size.
The non-crystalline solids alloy Fe that above-mentioned steps are obtained84Si10B6Microstructure carry out transmission electron microscope three-dimensionalreconstruction
Test characterization, resulting 3-D image are shown in Fig. 3, and the cluster to wherein size less than 1 nanometer carries out statistical average, obtain cluster
Average-size is 0.51 nanometer, almost the same with selected average atom cluster size.It is calculated and is tied by binary probability-distribution function
Fruit Fig. 2 is it is found that the first neighbour peak is since 0.2 nanometer, and the first neighbour peak and the second neighbour peak have a degree of overlapping, press
Downward trend according to first neighbour's tail of the peak portion can estimate the first neighbour peak termination locations close to 0.4 nanometer.Here atomic distance
From the distance between atom center is referred to, the size of entire atom is not calculated.For example, the atomic radius of Fe (iron) is
0.127 nanometer, diameter is 0.254 nanometer, and the atomic radius of B (boron) is 0.095 nanometer, and diameter is 0.19 nanometer.Fe and B are direct
The distance between center is 0.222 nanometer (after key and effect occur between them, the distance between center is less than when contact
0.222 nanometer), and the outermost distance from the outermost of Fe to B is 0.444 nanometer.Therefore, former by first neighbour's atomic building
The minimum dimension of sub- cluster is 0.4 nanometer.Equally by the first neighbour peak termination locations close to 0.4 nanometer it is found that the first neighbour is former
Maximum distance between son is about 0.4 nanometer, when first neighbour's atom is radius constituting atom cluster with 0.4 nanometer, the original
The diameter of sub- cluster is equal to the 2X0.4 nanometer length plus outermost 2 atomic radiuses, and about 1 nanometer.Therefore close with first
For the corresponding elementide size in adjacent peak between 0.4-1 nanometers, this has also determined that the elementide size progress to experimental observation
The range of statistics.It is noted that atom may be ionic condition, and the size of ion is far small after in view of composition cluster
In atom, so the lower limit of cluster size is less than 0.4 nanometer, so in statistical average cluster size, not to cluster size
Lower limit make limitation.
Embodiment 2
A kind of regulation method of amorphous alloy average atom cluster size, specific steps are as follows:
Step 1, Fe is calculated84Si10B6(index number in chemical formula is at%) amorphous alloy melt average atom cluster
Size with melt temperature variation: first with molecular dynamics or with first principle molecular dynamics simulation calculate
Fe84Si10B6The pair distribution of alloy melt with melt temperature variation, then to first neighbour's peak area of different temperatures
It is calculated, obtains the average atom ligancy elementide average-size corresponding with the ligancy of the first neighbour layer, and
The calculated result that average atom cluster size changes with melt temperature, in this, as the foundation of selection average atom cluster size；
Step 2, Fe is determined according to average atom cluster size84Si10B6The Overheating Treatment temperature of alloy melt: first with
Fe84Si10B6It is put down corresponding to 1300 DEG C of the calculated result selection that alloy melt average atom cluster size changes with melt temperature
Equal elementide size is about 0.58 nanometer, and by 1300 DEG C of Overheating Treatment temperature as melt；
Step 3, in the temperature of setting to Fe84Si10B6Alloy melt is heated: being set according to calculated result
Fe84Si10B6The Overheating Treatment temperature of melt, first by Fe84Si10B6Alloy melt is heated to setting with 10 DEG C/min of speed
1300 DEG C of Overheating Treatment temperature, 2 hours then are kept the temperature, to make Fe84Si10B6The average atom cluster size of melt reaches and counts
Calculate the identical stable state of result；
Step 4, by the Fe after heat treatment84Si10B6Alloy melt, which quickly solidifies, obtains non-crystalline solids alloy thin band: will
Fe after 1300 DEG C of Overheating Treatments84Si10B6Alloy melt is continuously pouring on high-speed rotating rapid cooling copper roller by nozzle,
The linear velocity of the copper roller surface is 25 meter per seconds, and alloy melt is by quick solidification at a thickness of 22 microns after 1300 DEG C of Overheating Treatments
Amorphous alloy ribbon, realize regulation to amorphous alloy ribbon average atom cluster size.
The non-crystalline solids alloy Fe that above-mentioned steps are obtained84Si10B6It is three-dimensional that the microstructure of strip carries out transmission electron microscope
Reconstruct test characterization, resulting 3-D image are shown in Fig. 4, and the cluster to wherein size less than 1 nanometer carries out statistical average, is rolled into a ball
The average-size of cluster is 0.59 nanometer, almost the same with selected average atom cluster size.
Embodiment 3
A kind of regulation method of amorphous alloy average atom cluster size, specific steps are as follows:
Step 1, Fe is calculated84Si10B6(index number in chemical formula is at%) amorphous alloy melt average atom cluster
Size with melt temperature variation: first with molecular dynamics or with first principle molecular dynamics simulation calculate
Fe84Si10B6The pair distribution of alloy melt with melt temperature variation, then to first neighbour's peak area of different temperatures
It is calculated, obtains the average atom ligancy elementide average-size corresponding with the ligancy of the first neighbour layer, and
The calculated result that average atom cluster size changes with melt temperature, in this, as the foundation of selection average atom cluster size；
Step 2, Fe is determined according to average atom cluster size84Si10B6The Overheating Treatment temperature of alloy melt: first with
Fe84Si10B6It is put down corresponding to 1500 DEG C of the calculated result selection that alloy melt average atom cluster size changes with melt temperature
Equal elementide size is about 0.54 nanometer, and by 1500 DEG C of Overheating Treatment temperature as melt；
Step 3, in the temperature of setting to Fe84Si10B6Alloy melt is heated: being set according to calculated result
Fe84Si10B6The Overheating Treatment temperature of melt, first by Fe84Si10B6Alloy melt is heated to setting with 10 DEG C/min of speed
1500 DEG C of Overheating Treatment temperature, 2 hours then are kept the temperature, to make Fe84Si10B6The average atom cluster size of melt reaches and counts
Calculate the identical stable state of result；
Step 4, by the Fe after heat treatment84Si10B6Alloy melt, which quickly solidifies, obtains non-crystalline solids alloy thin band: will
Fe after 1500 DEG C of Overheating Treatments84Si10B6Alloy melt is continuously pouring on high-speed rotating rapid cooling copper roller by nozzle,
The linear velocity of the copper roller surface is 25 meter per seconds, and alloy melt is by quick solidification at a thickness of 27 microns after 1500 DEG C of Overheating Treatments
Amorphous alloy ribbon, realize regulation to amorphous alloy ribbon average atom cluster size.
The non-crystalline solids alloy Fe that above-mentioned steps are obtained84Si10B6It is three-dimensional that the microstructure of strip carries out transmission electron microscope
Reconstruct test characterization, resulting 3-D image are shown in Fig. 5, and the cluster to wherein size less than 1 nanometer carries out statistical average, is rolled into a ball
The average-size of cluster is 0.55 nanometer, almost the same with selected average atom cluster size.
Embodiment 4
A kind of regulation method of amorphous alloy average atom cluster size, specific steps are as follows:
Step 1, Fe is calculated40Ni40P14B6(index number in chemical formula is at%) amorphous alloy melt average atom group
Cluster size with melt temperature variation: first with molecular dynamics or with first principle molecular dynamics simulation calculate
Fe40Ni40P14B6The pair distribution of alloy melt with melt temperature variation, then to the first neighbour peak of different temperatures
Area is calculated, and the average atom ligancy elementide average-size corresponding with the ligancy of the first neighbour layer is obtained,
And the calculated result that average atom cluster size changes with melt temperature, in this, as selection average atom cluster size according to
According to；
Step 2, Fe is determined according to average atom cluster size40Ni40P14B6The Overheating Treatment temperature of alloy melt: first
Utilize Fe40Ni40P14B6Alloy melt average atom cluster size selects 1300 DEG C of institutes right with the calculated result that melt temperature changes
The average atom cluster size answered is about 0.59 nanometer, and by 1300 DEG C of Overheating Treatment temperature as melt；
Step 3, in the temperature of setting to Fe40Ni40P14B6Alloy melt is heated: being set according to calculated result
Fe40Ni40P14B6The Overheating Treatment temperature of melt, first by Fe40Ni40P14B6Alloy melt is heated to set with 10 DEG C/min of speed
Then 1300 DEG C of fixed Overheating Treatment temperature keeps the temperature 2 hours, to make Fe40Ni40P14B6The average atom cluster size of melt
Reach stable state identical with calculated result；
Step 4, by the Fe after heat treatment40Ni40P14B6Alloy melt quickly solidifies that obtain non-crystalline solids alloy thin
Band: by the Fe after 1300 DEG C of Overheating Treatments40Ni40P14B6Alloy melt is continuously pouring to high-speed rotating fast quickly cooling by nozzle
But on copper roller, the linear velocity of the copper roller surface is 25 meter per seconds, and alloy melt is by quick solidification at thickness after 1300 DEG C of Overheating Treatments
For 27 microns of amorphous alloy ribbon, the regulation to amorphous alloy ribbon average atom cluster size is realized.
The non-crystalline solids alloy Fe that above-mentioned steps are obtained40Ni40P14B6The microstructure of strip carries out transmission electron microscope three
Dimension reconstruct test characterization, resulting 3-D image are shown in Fig. 6, and the cluster to wherein size less than 1 nanometer carries out statistical average, obtains
The average-size of cluster is 0.60 nanometer, almost the same with selected average atom cluster size.
In conclusion proposed by the present invention utilize melt elementide configuration and the micro- knot of regulating and controlling of quantities non-crystalline solids alloy
The process of structure can be realized the regulation to non-crystalline solids alloy microstructure, the non-crystalline solids suitable for different components
Alloy material system.The present invention achieves satisfied effect through validation trial.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of regulation method of amorphous alloy average atom cluster size characterized by comprising
The calculating step of amorphous alloy melt average atom cluster size: the average original of amorphous alloy melt under different temperatures is calculated
Sub- cluster size obtains the calculated result that average atom cluster size varies with temperature；
Overheating Treatment step is carried out to alloy melt: the average atom cluster size needed according to calculated result selection, it will
Temperature corresponding with selected average atom cluster size is determined as the Overheating Treatment temperature of alloy melt, in the overheat
The alloy melt is kept the temperature under treatment temperature, the alloy melt after obtaining Overheating Treatment；
Quick coagulation step: the amorphous alloy melt after the Overheating Treatment is quickly solidified, and obtains non-crystalline solids conjunction
Gold.
2. the regulation method of amorphous alloy average atom cluster size according to claim 1, which is characterized in that in institute
In the calculating step for stating amorphous alloy melt average atom cluster size, amorphous alloy melt is flat under the calculating different temperatures
The specific steps of equal elementide size are as follows: according to the pair distribution of amorphous alloy melt under different temperatures, calculate the
The area at one neighbour peak, obtain the first neighbour average atom ligancy and the average atom cluster size.
3. the regulation method of amorphous alloy average atom cluster size according to claim 2, which is characterized in that described
Pair distribution is calculated by molecular dynamics or/and first principle molecular dynamics simulation and is obtained.
4. the regulation method of amorphous alloy average atom cluster size according to claim 1, which is characterized in that calculate
The temperature range of the average atom cluster size of alloy melt is 1300-1800 DEG C.
5. the regulation method of amorphous alloy average atom cluster size according to claim 1, which is characterized in that in institute
It states and alloy melt is carried out in Overheating Treatment step, melted after determining the Overheating Treatment temperature of alloy melt and to the alloy
Before body is kept the temperature, the alloy melt is warming up to the Overheating Treatment temperature with 5-15 DEG C/min of rate.
6. the regulation method of amorphous alloy average atom cluster size according to claim 1, which is characterized in that described
Soaking time is 1.5-3 hours.
7. the regulation method of amorphous alloy average atom cluster size according to claim 1, which is characterized in that in institute
It states in quick coagulation step, it is described to be quickly solidified as completing by using high-speed plane stream caster technology；Preferably, the high speed
Planar flow continuous casting technology are as follows: be poured into the amorphous alloy melt on high-speed rotating chill roll described in progress by nozzle
Quickly solidification.
8. the regulation method of amorphous alloy average atom cluster size according to claim 7, which is characterized in that described
The linear velocity of cooling roller surface is 15-30 meter per second.
9. the regulation method of amorphous alloy average atom cluster size according to claim 7, which is characterized in that described
Non-crystalline solids alloy is thin ribbon shaped；Preferably, the non-crystalline solids alloy with a thickness of 18-32 microns；Preferably, described
The width of non-crystalline solids alloy is 50-282 millimeters.
10. the regulation method of amorphous alloy average atom cluster size according to claim 7, which is characterized in that institute
State non-crystalline solids alloy be amorphous alloy system in Fe base, FeNi base, FeCo base and iron-base nanometer crystal alloy amorphous
State alloy strip steel rolled stock presoma；It is highly preferred that the non-crystalline solids alloy is Fe84Si10B6。
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| CN112132785A (en) * | 2020-08-25 | 2020-12-25 | 华东师范大学 | Transmission electron microscope image recognition and analysis method and system for two-dimensional material |
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