CN100569984C - Crystalline state alloy spherical particle/amorphous alloy base composite material and preparation method thereof - Google Patents
Crystalline state alloy spherical particle/amorphous alloy base composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to amorphous composite design and technology of preparing, be specially a kind of crystalline state alloy spherical particle/amorphous alloy base composite material and preparation method thereof, solve problems such as the plasticity of amorphous alloy is very poor.Crystalline state alloy spherical particle/amorphous alloy base composite material comprises the immiscible alloy M-N that alloying element M and N form, and other alloying elements that add, other alloying elements and the miscible formation amorphous alloy of the alloying element M basal body structure that add, alloying element N is distributed in the amorphous alloy matrix with the sub-form disperse of crystalline state alloy spherical particle.Liquid-liquid phase took place earlier and becomes before glass transition takes place in alloy melt, generated the matrix liquid phase L of rich M
1Spherical droplets L with rich N
2, a liquid phase L wherein
2Be distributed in another liquid phase L with the spherical droplets form
1In the matrix; Subsequently fast in the process of cooling, matrix liquid phase L
1Glass transition taking place, solidify back spheroidal particle disperse and be distributed in the matrix, forms crystalline state spheroidal particle/amorphous alloy occurring matrix type matrix material.
Description
Technical field
The invention belongs to amorphous composite design and technology of preparing, specifically become the characteristics of metallurgy feature and alloy glass transition, design a kind of crystalline state alloy spherical particle/amorphous alloy base composite material and preparation method thereof in conjunction with the immiscible alloy liquid-liquid phase.
Background technology
Amorphous alloy (being metallic glass) has a series of excellent characteristic such as high strength, high rigidity, corrosion-resistant, isotropy, is with a wide range of applications in fields such as automobile, aerospace, electronics, machinery, medical material, sports goodss.Usually, the formation condition of amorphous alloy is 10
4～10
6Under the K/s speed of cooling, alloy melt is cooled to be lower than its glass transformation temperature T
g, make alloy melt avoid taking place crystal forming core and crystallization, thereby rapid solidification forms non-crystalline state (or vitreous state) alloy.Along with quick refrigerative technology improves constantly, after the diversification by the alloy constituent element and the optimization design of alloy composition, obtained swift and violent development in the block metal glass size or on the amorphous alloy kind no matter be.Investigators have discovered multiple amorphous alloy successively, as Cu base, Fe base, Ca base, Al base, La base, Zr base, Pd base, Co base, Ti base, Ni base, Y base etc.Up to the present, the alloy system that critical diameter can reach 10mm has Cu base, Fe base, La base, Zr base, Pd base, Ti base, Pt base, Y base, Mg base, Ca base etc., wherein Pd
40Cu
30Ni
10P
20Be the strongest alloy of glass forming ability, critical diameter reaches 72mm, the block metal glass of the size maximum that this is so far to be reported.
Although amorphous alloy has very high yield strength, elastic strain limit and higher fracture toughness property, the plasticity of amorphous alloy is very poor, and it is greatly limited in exploitation and application.This also is the great research topic of pendulum in face of investigators and the difficult problem of urgent need solution.The method that solves this difficult problem is exactly to introduce the crystalline state phase in non-crystaline amorphous metal, promote to form multiple shear bands, further strengthen the amorphous alloy matrix, improve its toughness and plasticity, promptly form toughness and plasticity preferably second mutually particle dispersion be distributed in amorphous composite in the alloy substrate.The current approach of introducing the crystalline state phase mainly contains three kinds, and the first makes by annealing thermal treatment and produces some nanoscale crystalline state phases in the single non-crystaline amorphous metal; It two is to add toughness and plasticity particle preferably in amorphous alloy; The third approach is that the amorphous alloy melt is given birth to dendrite in before glass transition.Yet these three kinds of approach respectively have relative merits, and the crystalline state phase size of first kind of approach acquisition is too little, the difficult control of technology; Second kind of approach is difficult to make the even particle distribution that adds, and also exists particle to combine problem with basal body interface; The third approach can only obtain head and analyse dendrite phase volume fraction and the less matrix material of size, otherwise can increase the viscosity of alloy melt, reduces casting rate greatly, causes the alloy melt crystallization.Add in second and third approach or interior living solid phase all can influence the alloy melt glass forming ability.In addition, annealing thermal treatment, the type of matrix material of method preparation that adds particle and Nei Sheng dendrite are single.
Summary of the invention
The object of the present invention is to provide a kind of crystalline state alloy spherical particle/amorphous alloy base composite material and preparation method thereof, solve problems such as the plasticity of amorphous alloy is very poor.
Technical scheme of the present invention is:
A kind of crystalline state alloy spherical particle/amorphous alloy base composite material, comprise the immiscible alloy M-N that alloying element M and N form, and other alloying elements that add, liquid-liquid phase at first takes place in the alloy melt process of cooling to be become, other alloying elements that add and the amorphous alloy basal body structure of the rich M of the miscible formation of alloying element M, the amorphous alloy matrix of rich M mutually in, all shared than the alloying element M ratio of arbitrary other alloying elements is little, and alloying element M and the alloying element sum of the interpolation shared atomic ratio of rich M in mutually is 75～95%; Alloying element N is distributed in the amorphous alloy matrix with the spheroidal particle form disperse of the rich N of crystal alloy, the spheroidal particle of rich N mutually in, the shared atomic ratio of alloying element N is 60～95%; Diameter range 10 nanometers of spheroidal particle N～100 microns, percent by volume is 1～50%.
Described crystalline state alloy spherical particle/amorphous alloy base composite material, immiscible alloy M-N are preferably one of Al-Pb, Al-Bi, Al-In, Al-Cd, Ca-Gd, Ca-Na, Ce-V, Cu-Li, Cu-Nb, Cu-Fe, Cu-Co, Cu-Ta, Cu-Pb, Cu-Bi, Cu-W, Fe-In, Fe-Sn, Fe-Sr, Mg-Na, Ni-Pb, Ni-Ag, Sc-V, Sm-Ba, Ti-Gd, Y-V, Y-Cr alloy.
Described crystalline state alloy spherical particle/amorphous alloy base composite material, other alloying elements of interpolation are and one or more of the corresponding non-crystaline amorphous metal system of alloying element M composition other alloying elements of interpolation and the enthalpy of mixing Δ H between the alloying element M
Mix -For negative, the rich M matrix liquid phase alloy of miscible other alloying elements that add is 10～10
6Glass transition takes place under the K/s speed of cooling.
Described crystalline state alloy spherical particle/amorphous alloy base composite material, alloying element M and N be awkward miscible alloy system under liquid state, immiscible alloy be between the constituent element enthalpy of mixing for just, repel mutually between the constituent element atom, immiscible alloy when liquid, other alloying elements and the alloying element N that add are immiscible under liquid state, and rich N liquid phase is 10～10
6Glass transition does not take place under the K/s speed of cooling.
The preparation method of described crystalline state alloy spherical particle/amorphous alloy base composite material comprises the steps:
(1) has the metallurgy feature in liquid constituent element unmixing zone based on immiscible alloy, select and the optimization of Chemical Composition design, make alloy melt before glass transition takes place, liquid-liquid phase takes place earlier become, generate the matrix liquid phase L of rich M by alloy species
1Spherical droplets L with rich N
2, a liquid phase L wherein
2Be distributed in another liquid phase L with the spherical droplets form
1In the matrix;
(2) subsequently fast in the process of cooling, the speed of cooling 10～10 of alloy melt
6K/s, matrix liquid phase L
1Glass transition takes place, liquid phase L
2Spheroidal particle disperse after solidifying is distributed in the matrix, forms crystalline state spheroidal particle/amorphous alloy occurring matrix type matrix material.
The invention has the beneficial effects as follows:
The present invention is based on immiscible alloy and have the metallurgy feature in liquid constituent element unmixing zone, select and the optimization of Chemical Composition design, make alloy melt before glass transition takes place, liquid-liquid phase takes place earlier become, generate the matrix liquid phase L of rich M by alloy species
1Spherical droplets L with rich N
2, a liquid phase L wherein
2Be distributed in another liquid phase L with the spherical droplets form
1In the matrix; Can prepare crystalline state alloy spherical particle/amorphous alloy base composite material with alloy designs as required, not only simplify, shortened the preparation process and the cost of such matrix material, and indicate direction for development of new high-performance amorphous composite.Introducing the optimal method of second phase particle formation matrix material in alloy is to make alloy melt generation glass transition generate the liquid phase drop.This can reduce the glass forming ability influence to alloy on the one hand, and the second phase particle can be uniformly distributed in the matrix after guaranteeing to solidify; On the other hand, solidify between the back second phase particle and matrix combine better.Especially, be spherical behind the liquid phase droplet solidification of generation, this spherical crystalline state particle can more much easier generation multiple shear bands than dendrite, and the plasticity of material is better.
Description of drawings
Fig. 1 (a)-(b) becomes the schematic diagram for preparing amorphous composite for the present invention is based on the immiscible alloy liquid-liquid phase.
Fig. 2 selects and principle of design figure for the alloy of crystalline state alloy spherical particle of the present invention/amorphous alloy occurring matrix type matrix material.
Fig. 3 (a)-(c) is the x-ray diffraction pattern (Cu target) of the strip of alloy single roller rapid quenching method preparation of the present invention; Wherein, Fig. 3 (a) is embodiment 1, and composition is Cu
30Fe
56Si
7B
7Fig. 3 (b) is embodiment 2, and composition is Al
80.75Pb
5Ni
4.75Y
7.6Co
1.9Fig. 3 (c) is embodiment 3, composition Cu
25Fe
45Zr
10B
20
Fig. 4 (a)-(c) is the scanning electron microscopy phase (SEM) (back scattering pattern) of the strip of alloy single roller rapid quenching method preparation of the present invention; Wherein, Fig. 4 (a) is embodiment 1, and composition is Cu
30Fe
56Si
7B
7Fig. 4 (b) is embodiment 2, and composition is Al
80.75Pb
5Ni
4.75Y
7.6Co
1.9Fig. 4 (c) is embodiment 3, and composition is Cu
25Fe
45Zr
10B
20
Embodiment
The invention provides the technology of preparing of novel amorphous composite, the metallurgy feature that has liquid constituent element unmixing zone based on immiscible alloy, select and the optimization of Chemical Composition design by alloy species, can obtain crystalline state alloy spherical particle/amorphous alloy occurring matrix type, amorphous alloy spherical particle/crystal alloy occurring matrix type and amorphous alloy spherical particle/three kinds of dissimilar matrix materials of amorphous alloy occurring matrix type.Its characteristics were alloy melt before glass transition takes place, and the single-phased alloy melt liquid-liquid phase at first takes place becomes, and generates two immiscible liquid phase L
1And L
2, a liquid phase L wherein
2Be distributed in another liquid phase L with the spherical droplets form
1In the matrix; Subsequently fast in the process of cooling, matrix liquid phase L
1Or disperse drop L
2Glass transition takes place, even two liquid phase L
1And L
2Glass transition all takes place, solidify the back and form three kinds of dissimilar matrix materials, shown in Fig. 1 (a)-(b), alloy melt is cooled to liquid constituent element unmixing zone, liquid-liquid phase becomes and to start from the drop forming core, liquid nuclear continue to grow up by the solute diffusion and drop and drop between coalescence and alligatoring.In quick process of cooling, matrix liquid phase L
1Or spherical droplets L
2Glass transition takes place, even two liquid phase L
1And L
2Glass transition all takes place, and solidifies the back and forms three kinds of dissimilar amorphous composites.
Described crystalline state alloy spherical particle/amorphous alloy occurring matrix type matrix material is at first chosen suitable immiscible alloy system on alloy is selected and designed.The universal expression formula of immiscible alloy is M-N, and M and N represent the alloying element of immiscible alloy respectively, and liquid-liquid phase becomes the matrix liquid phase L that the back generates rich M
1The spherical droplets L of (percent by volume is greater than 50%) and rich N
2(percent by volume is less than 50%).Rich M is meant the liquid phase of mainly being made up of alloying element M, rich M mutually in, the shared atomic ratio of the alloying element sum of alloying element M and interpolation is 75～100%, all the other are alloying element N; Rich N is meant the liquid phase of mainly being made up of alloying element N, the spheroidal particle of rich N mutually in, the shared atomic ratio of alloying element N is 60～100%, all the other are the alloying element of alloying element M and interpolation.Require to have bigger positive enthalpy of mixing Δ H between immiscible alloy constituent element M and the N element
Mix +, two constituent elements are immiscible or solubleness is very little when liquid state.Then, on the basis of choosing immiscible alloy M-N, choose again other alloying elements x that will add, y, z etc. (other alloying element represents with x, y, z, other alloying elements of interpolation be one or more all can, this depends on the kind of immiscible alloy M-N).When choosing alloying element x, y, z etc., require alloying element M, x, y, z etc. to have bigger negative enthalpy of mixing Δ H arbitrarily between the two
Mix -, the atomic radius difference is usually greater than 12%, their can complete miscibility when liquid, sees synoptic diagram 2.But, be dissolved in hardly among the immiscible alloy constituent element N during liquid state such as alloying element x, y, z, and almost all be dissolved among the immiscible alloy constituent element M.By alloy designs and optimization alloy composition, make the rich M matrix liquid phase of having dissolved alloying element x, y, z etc. have stronger glass forming ability.Under condition of fast cooling, liquid-liquid phase becomes two liquid phases that generate, rich M matrix liquid phase L
1Glass transition takes place in (having dissolved alloying element x, y, z etc.), generates amorphous alloy Mxyz, but the spherical droplets L of rich N
2Glass transition does not take place in (almost not dissolving alloying element x, y, z), can only generate the spheroidal particle of crystalline state.The matrix liquid phase L of rich M
1Spherical droplets L with rich N
2After solidifying, the rich N spheroidal particle of crystalline state is uniformly distributed in the Mxyz amorphous alloy matrix of rich M, forms crystalline state alloy spherical particle/amorphous alloy occurring matrix type matrix material.Give birth to the matrix material of crystalline state spheroidal particle in comprising in this non-crystaline amorphous metal matrix, can around spheroidal particle, can produce multiple shear bands, more help the plastic deformation and the reinforcement of non-crystaline amorphous metal matrix than interior living dendrite.When crystalline state spheroidal particle during for softer phase (Pb, Bi etc.), this crystalline state spheroidal particle/amorphous alloy-based composite material has good self-lubricating property, can be used as the high-abrasive material of accurate apparatus.
The M-N immiscible alloy of described crystalline state alloy spherical particle/amorphous alloy occurring matrix type matrix material is preferably Al-Pb, Al-Bi, Al-In, Al-Cd, Ca-Na, Ca-Gd, Cu-Li, Cu-Nb, Cu-Fe, Cu-Co, Cu-Ta, Cu-Pb, Cu-Bi, Cu-W, Fe-Sn, Fe-In, Fe-Sr, Mg-Na, Ni-Ag, Ni-Pb, Ti-La, Ti-Gd alloy.Other alloying elements that add are and the corresponding non-crystaline amorphous metal system of alloying element M composition, as:
Among the immiscible alloy Al-Pb, the alloying element of interpolation can be Ni, Y, Co, the expression formula Al of matrix amorphous alloy component
aNi
bY
cCo
d(atomic ratio), a=80～90%, b=1～10%, c=4～10%, d=1～5%, a+b+c+d=100, any enthalpy of mixing Δ H between the two of the alloying element of alloy element Al and interpolation
Mix -Be 0～-38kJ/mol;
Among the immiscible alloy Ca-Na, the alloying element of interpolation can be Mg, Zn, the expression formula Ca of matrix amorphous alloy component
aMg
bZn
c(atomic ratio), a=60～70%, b=10～20%, c=10～30%, a+b+c=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element Ca and interpolation
Mix -For-13～-72kJ/mol;
Among the immiscible alloy Cu-Li, the alloying element of interpolation can be Zr, Hf, the expression formula Cu of matrix amorphous alloy component
aZr
bHf
c(atomic ratio), a=40～60%, b=0～60%, c=0～60%, a+b+c=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element cu and interpolation
Mix -Be 0～-92kJ/mol;
Among the immiscible alloy Cu-Nb, the alloying element of interpolation can be Hf, Ti, the expression formula Cu of matrix amorphous alloy component
aHf
bTi
c(atomic ratio), a=50～70%, b=20～30%, c=10～20%, a+b+c=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element cu and interpolation
Mix -Be 0～-17kJ/mol;
Among the immiscible alloy Cu-Ta, the alloying element of interpolation can be Zr, Ti, the expression formula Cu of matrix amorphous alloy component
aZr
bTi
c(atomic ratio), a=50～70%, b=20～40%, c=5～15%, a+b+c=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element cu and interpolation
Mix -Be 0～-92kJ/mol;
Among the immiscible alloy Fe-Sn, the alloying element of interpolation can be Si, B, the expression formula Fe of matrix amorphous alloy component
aSi
bB
c(atomic ratio), a=75～85%, b=5～15%, c=5～15%, a+b+c=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element Fe and interpolation
Mix -For-84～-96kJ/mol;
Among the immiscible alloy Mg-Na, the alloying element of interpolation can be Cu, Ni, Ag, Zn, Y, Gd, the expression formula Mg of matrix amorphous alloy component
aCu
bNi
cAg
dZn
eY
fGd
g(atomic ratio), a=60～70%, b=5～10%, c=5～10%, d=3～7%, e=3～7%, f=3～7%, g=3～7%, a+b+c+d+e+f+g=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element Mg and interpolation
Mix -For-4～-88kJ/mol;
Among the immiscible alloy Ni-Ag, the alloying element of interpolation can be Fe, B, Si, Nb, the expression formula Ni of matrix amorphous alloy component
aFe
bB
cSi
dNb
e(atomic ratio), a=40～50%, b=25～30%, c=15～25%, d=1～9%, e=1～7%, a+b+c+d+e=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element Ni and interpolation
Mix -For-8～-104kJ/mol;
Among the immiscible alloy Ti-La, the alloying element of interpolation can be Zr, Cu, Ni, Be, the expression formula Ti of matrix amorphous alloy component
aZr
bCu
cNi
dBe
e(atomic ratio), a=40～60%, b=20～30%, c=10～15%, d=0～5%, e=15～25%, a+b+c+d+e=100, any enthalpy of mixing Δ H between the two of the alloying element of alloying element Ti and interpolation
Mix -For-9～-196kJ/mol;
The spheroidal particle diameter range is 10 nanometers to 100 micron (are preferably 10 nanometers～50 micron) in described crystalline state alloy spherical particle/amorphous alloy occurring matrix type matrix material, these spheroidal particle disperses are distributed in the amorphous alloy matrix, the percent by volume 1～50% (being preferably 20～40%) that spheroidal particle is shared.By the selection of alloy species and the optimization and the design of alloy composition, the mean sizes of spheroidal particle kind, matrix alloy kind, spheroidal particle, the percent by volume that particle accounts for and the distribution in matrix thereof can change according to different service requirementss.
The invention provides the method for design of crystalline state alloy spherical particle/amorphous alloy occurring matrix type matrix material, matrix material can be mixed with in the synthetic method any one or a few to make and is used for obtaining by multiple preparation, this depends on required material forms, as powder, thin slice, strip, ingot casting, plate etc.(1) can be prepared into the gram level to feather weight thin slice, thin band material (20～900 microns of thickness) in batches by single roller melt-spun method, can obtain the gram level to feather weight composite material powder in batches by methods such as gas atomization or mechanical alloyings.The alloy stronger to some glass forming ability can directly be prepared into thickness at millimetre-sized block materials by the melt cast method.(2) before glass transition, alloy cooling pass through liquid constituent element unmixing temperature because of between than hour, under condition of fast cooling, the spheroidal particle and the disperse that can obtain nano-grade size are distributed in the amorphous alloy matrix.
With block materials (purity is higher than 99.9%) such as the rod of Fe-B master alloy and commercially available pure metal Cu, Fe, Si, B element, piece, ingot, plates is parent material, arc melting becomes master alloy ingot under the argon gas atmosphere of process titanium passivation, alloying constituent (atomic percent, down together) is Cu
30Fe
56Si
7B
7Master alloy ingot needs repeatedly arc melting for several times to guarantee the homogeneity of composition.Get an amount of mother alloy material and be positioned in the quartz crucible that has nozzle, (speed of cooling is 10 with single-roller rapid quenching with quenching with alloy melt after the induction heating refuse under argon gas atmosphere
4～10
6K/s) be prepared into strip.The internal diameter of quartz crucible is 14mm, and the diameter of nozzle is 0.7mm, and the spacing of nozzle and single roll surface is 0.3mm, and single roller linear velocity is 50m/s.The strip width of single-roller rapid quenching with quenching preparation is about 3mm, and its thickness is 20～40 microns.Strip is used for scanning electronic microscope (SEM) observation after mechanical polishing and X-ray diffraction (XRD) is analyzed.XRD, SEM the results are shown in Figure 3a and Fig. 4 a.The result shows, strip is by the spherical rich Cu particle of crystalline state (in the rich Cu particle, the Cu atomic ratio accounts for 84.5%, all the other are Fe, Si, B element, and the Fe atomic ratio accounts for 8.7%, and the Si atomic ratio accounts for 1.8%, the B atomic ratio accounts for 5%) and the rich Fe-Si-B alloy substrate of non-crystalline state (in the rich Fe-Si-B alloy substrate, element of Fe, Si, B alloy atom ratio account for 91.3%, and all the other are the Cu element) to form, the crystalline state spheroidal particle is distributed in the non-crystaline amorphous metal matrix uniformly.XRD and SEM studies show that, glass transition takes place before, the liquid-liquid phase change has taken place in the alloy melt process of cooling, rich Cu spherical droplets and rich Fe matrix liquid phase have been generated, because elements Si, B combine with Fe, and the metallic glass transformation takes place, so formed crystalline state spheroidal particle/amorphous alloy matrix composite.The percent by volume of the rich Cu spheroidal particle of crystalline state is about 27%, the diameter of spheroidal particle in 100 nanometers in 2 micrometer ranges.
Experimental result shows that the FeSiB amorphous alloy-based composite material is become by liquid-liquid phase introduces interior green-ball shape crystalline state Cu particle, and the process of this acquisition crystalline state Cu particle is less to the glass transition influence of FeSiB alloy.The Cu particle derives from the product that liquid-liquid phase becomes, and FeSiB non-crystaline amorphous metal matrix combines better with the Cu particle behind the alloy graining, and crystalline state Cu particle can be uniformly distributed in the amorphous FeSiB alloy substrate.Especially, liquid-liquid phase is sphere after becoming the liquid Cu droplet solidification that generates, again because Cu this as face-centered cubic crystal structure, crystalline state Cu particle/FeSiB amorphous alloy-based composite material is in the compressive set process, around spherical crystalline state Cu particle, can produce more multiple shear bands than dendrite Cu, therefore, crystalline state Cu particle/FeSiB amorphous alloy-based composite material has better plasticity.
With block materials (purity is higher than 99.9%) such as the rod of commercially available pure metal Al, Pb, Ni, Y, Co element, piece, ingot, plates is parent material, uses the melting method identical with embodiment 1 to prepare Al
80.75Pb
5Ni
4.75Y
7.6Co
1.9Mother alloy, (speed of cooling is 10 to use the single-roller rapid quenching with quenching identical with embodiment 1 to prepare strip
4～10
6K/s).XRD, SEM the results are shown in Figure 3b and Fig. 4 b.The result shows, strip is by the rich AlNiCoY alloy substrate of amorphous (in the rich AlNiCoY alloy substrate, element al, Ni, Co, Y sum account for 98.6% of matrix atomic ratio, all the other are the Pb element) and the rich Pb spheroidal particle of crystalline state (in the rich Pb spheroidal particle, the Pb atomic ratio accounts for 97.4%, all the other are Al, Ni, Co, Y element, the Al atomic ratio accounts for 0.2%, the Ni atomic ratio accounts for 0.7%, the Co atomic ratio accounts for 0.12%, the Y atomic ratio accounts for 1.58%) to form, the crystalline state particle is distributed in the non-crystaline amorphous metal matrix uniformly.XRD and SEM studies show that, glass transition takes place before, the liquid-liquid phase change has taken place in the alloy melt process of cooling, rich Al of matrix and spherical rich Pb two liquid phases have been generated, because element Ni, Co, Y combine with Al, and the metallic glass transformation takes place, so formed mutually richer Pb crystalline state spheroidal particle/amorphous alloy matrix composite.The percent by volume of the rich Pb spheroidal particle of crystalline state is about 10%, the diameter of spheroidal particle in 50 nanometers in 1 micrometer range.
Experimental result shows that the AlNiCoY amorphous alloy-based composite material is become by liquid-liquid phase introduces interior green-ball shape crystalline state Pb particle, and the process of this acquisition crystalline state Pb particle is less to the glass transition influence of AlNiCoY alloy.The Pb particle derives from the product that liquid-liquid phase becomes, and AlNiCoY non-crystaline amorphous metal matrix combines better with the Pb particle behind the alloy graining, and crystalline state Pb particle can be uniformly distributed in the amorphous Al NiCoY alloy substrate.Especially, liquid-liquid phase is sphere after becoming the liquid phase P b droplet solidification that generates, again because Pb this as face-centered cubic crystal structure, crystalline state Pb particle/AlNiCoY amorphous alloy-based composite material can produce the more multiple shear bands than dendrite Cu around spherical crystalline state Cu particle in the compressive set process; In addition, because crystalline state Pb particle is soft, and matrix is the very high AlNiCoY non-crystaline amorphous metal of intensity and hardness.Therefore, crystalline state Pb particle/AlNiCoY amorphous alloy-based composite material not only has better plasticity and also has good self-lubricating, wear resistance.
With block materials (purity is higher than 99.9%) such as the rod of Fe-B master alloy and commercially available pure metal Cu, Fe, Zr, B element, piece, ingot, plates is parent material, uses the mother alloy melting method identical with embodiment 1 to prepare Cu
25Fe
45Zr
10B
20Alloy, (speed of cooling is 10 to use the single-roller rapid quenching with quenching identical with embodiment 1 to prepare strip
4～10
6K/s).XRD, SEM the results are shown in Figure 3c and Fig. 4 c.The result shows, strip is by the rich FeZrB alloy substrate of non-crystalline state (in the rich FeZrB alloy substrate, element of Fe, Zr, B sum account for 88.7% of matrix atomic ratio, all the other are the Cu element) and the rich Cu spheroidal particle of crystalline state (in the rich Cu spheroidal particle, the Cu atomic ratio accounts for 82.1%, and all the other are Fe, Zr, B element, the Fe atomic ratio accounts for 7.5%, the Zr atomic ratio accounts for 5.6%, and the B atomic ratio accounts for 4.8%) to form, the crystalline state spheroidal particle is uniformly distributed in the non-crystalline state FeZrB alloy substrate.XRD and SEM studies show that, glass transition takes place before, the liquid-liquid phase change has taken place in the alloy melt process of cooling, rich Fe of matrix and spherical rich Cu two liquid phases have been generated, because element Zr, B combine with Fe, and the metallic glass transformation takes place, so formed the spherical crystalline state particle of rich Cu/non-crystaline amorphous metal matrix composite.The volume fraction of the rich Cu spheroidal particle of crystalline state is about 21%, the diameter of spheroidal particle in 90 nanometers in 1 micrometer range.
Experimental result shows that the FeZrB amorphous alloy-based composite material is become by liquid-liquid phase introduces interior green-ball shape crystalline state Cu particle, and the process of this acquisition crystalline state Cu particle is less to the glass transition influence of FeZrB alloy.The Cu particle derives from the product that liquid-liquid phase becomes, and FeZrB non-crystaline amorphous metal matrix combines better with the Cu particle behind the alloy graining, and crystalline state Cu particle can be uniformly distributed in the amorphous FeZrB alloy substrate.Especially, liquid-liquid phase is sphere after becoming the liquid Cu droplet solidification that generates, again because Cu this as face-centered cubic crystal structure, crystalline state Cu particle/FeZrB amorphous alloy-based composite material is in the compressive set process, around spherical crystalline state Cu particle, can produce more multiple shear bands than dendrite Cu, therefore, crystalline state Cu particle/FeZrB amorphous alloy-based composite material has better plasticity.
With block materials (purity is higher than 99.9%) such as the rod of commercially available pure metal Cu, Li, Zr element, piece, ingots is parent material, uses the mother alloy melting method identical with embodiment 1 to prepare Cu
25Li
50Zr
25Alloy, (speed of cooling is 10 to use the single-roller rapid quenching with quenching identical with embodiment 1 to prepare strip
4～10
6K/s).In quick process of cooling, because Cu-Li is an immiscible alloy, liquid-liquid phase at first takes place and becomes in the single-phased alloy melt, and Li-Zr alloy complete unmixing when liquid state.Complete miscibility when other alloys Zr that adds and alloying element cu are liquid.Cu
25Li
50Zr
25Alloy melt generation liquid-liquid phase becomes rich Cu liquid phase of generation (having dissolved other elements Zr that adds) and rich Li liquid phase, and under condition of fast cooling, rich Cu liquid phase generation glass transition generates CuZr non-crystaline amorphous metal matrix; Rich Li spherical droplets generation crystallization forms spherical rich Li particle.Therefore, the strip of single roller rapid quenching preparation is by the rich CuZr alloy substrate of non-crystalline state (in the rich CuZr alloy substrate, element Cu, Zr sum account for 86.6% of matrix atomic ratio, all the other are the Li element) and the rich Li spheroidal particle of crystalline state (in the rich Li spheroidal particle, the Li atomic ratio accounts for 95.3%, all the other are Cu, Zr element, the Cu atomic ratio accounts for 3.9%, the Zr atomic ratio accounts for 0.8%) form, the crystalline state spheroidal particle is uniformly distributed in the amorphous Cu Zr alloy substrate, has formed the spherical crystalline state particle of rich Li/non-crystaline amorphous metal matrix composite.The volume fraction of the rich Li spheroidal particle of crystalline state is about 48%, the diameter of spheroidal particle at 0.5 micron in 20 micrometer ranges.
Experimental result shows that the CuZr amorphous alloy-based composite material is become by liquid-liquid phase introduces interior green-ball shape crystalline state Li particle, and the process of this acquisition crystalline state Li particle is less to the glass transition influence of CuZr alloy.The Li particle derives from the product that liquid-liquid phase becomes, and CuZr non-crystaline amorphous metal matrix combines better with the Li particle behind the alloy graining, and crystalline state Li particle can be uniformly distributed in the amorphous CuZr alloy substrate.Especially, liquid-liquid phase is sphere after becoming the liquid phase Li droplet solidification that generates, again because Li this as body-centered cubic crystal structure, crystalline state Li particle/CuZr amorphous alloy-based composite material is in the compressive set process, around spherical crystalline state Li particle, can produce more multiple shear bands than dendrite Li, therefore, crystalline state Li particle/CuZr amorphous alloy-based composite material has better plasticity.
Embodiment 5
With block materials (purity is higher than 99.9%) such as the rod of commercially available pure metal Ni, Ag, Fe, B, Si, Nb element, piece, ingot, plates is parent material, uses the mother alloy melting method identical with embodiment 1 to prepare Ni
30.24Ag
30Fe
20.16B
13.44Si
3.36Nb
2.8Alloy, (speed of cooling is 10 to use the single-roller rapid quenching with quenching identical with embodiment 1 to prepare strip
4～10
6K/s).In quick process of cooling, because Ni-Ag is an immiscible alloy, liquid-liquid phase at first takes place and becomes in the single-phased alloy melt, and other alloys Fe of interpolation, B, Si, Nb are not dissolved in the rich Ag liquid phase, and are dissolved in the rich Ni liquid phase.Ni
30.24Ag
30Fe
20.16B
13.44Si
3.36Nb
2.8Alloy melt generation liquid-liquid phase becomes rich Ni liquid phase of generation (having dissolved other element of Fe, B, Si, the Nb that add) and rich Ag liquid phase, and under condition of fast cooling, rich Ni liquid phase generation glass transition generates NiFeBSiNb non-crystaline amorphous metal matrix; Rich Ag spherical droplets generation crystallization forms spherical rich Ag particle.Therefore, the strip of single roller rapid quenching preparation is by the rich NiFeBSiNb alloy substrate of non-crystalline state (in the rich NiFeBSiNb alloy substrate, element Ni, Fe, B, Si, the Nb sum accounts for 94.7% of matrix atomic ratio, all the other are the Ag element) and the rich Ag spheroidal particle of crystalline state (in the rich Ag spheroidal particle, the Ag atomic ratio accounts for 92.5%, all the other are Ni, Fe, B, Si, the Nb element, the Ni atomic ratio accounts for 1.2%, the Fe atomic ratio accounts for 0.8%, the B atomic ratio accounts for 1.4%, the Si atomic ratio accounts for 2.7%, the Nb atomic ratio accounts for 1.4%) form, the crystalline state spheroidal particle is uniformly distributed in the non-crystalline state NiFeBSiNb alloy substrate, has formed the spherical crystalline state particle of rich Ag/non-crystaline amorphous metal matrix composite.The volume fraction of the rich Ag spheroidal particle of crystalline state is about 20%, the diameter of spheroidal particle at 0.2 micron in 25 micrometer ranges.
Experimental result shows that the NiFeBSiNb amorphous alloy-based composite material is become by liquid-liquid phase introduces interior green-ball shape crystalline state Ag particle, and the process of this acquisition crystalline state Ag particle is less to the glass transition influence of NiFeBSiNb alloy.The Ag particle derives from the product that liquid-liquid phase becomes, and NiFeBSiNb non-crystaline amorphous metal matrix combines better with the Ag particle behind the alloy graining, and crystalline state Ag particle can be uniformly distributed in the amorphous NiFeBSiNb alloy substrate.Especially, liquid-liquid phase is sphere after becoming the liquid phase Ag droplet solidification that generates, again because Ag this as face-centered cubic crystal structure, crystalline state Ag particle/NiFeBSiNb amorphous alloy-based composite material is in the compressive set process, around spherical crystalline state Ag particle, can produce more multiple shear bands than dendrite Ag, therefore, crystalline state Ag particle/NiFeBSiNb amorphous alloy-based composite material has better plasticity.
Claims (4)
1, a kind of crystalline state alloy spherical particle/amorphous alloy base composite material, it is characterized in that: comprise the immiscible alloy M-N that alloying element M and N form, and other alloying elements that add, form rich M amorphous alloy matrix and rich N crystalline state alloy spherical particle, in the rich M amorphous alloy matrix, all shared than the alloying element M ratio of arbitrary other alloying elements is little, and the atomic ratio of the shared rich M amorphous alloy matrix of alloying element sum of alloying element M in the rich M amorphous alloy matrix and interpolation is 75～95%; Alloying element N is distributed in the rich M amorphous alloy matrix with the sub-form disperse of rich N crystalline state alloy spherical particle, and in rich N crystalline state alloy spherical particle, the shared atomic ratio of alloying element N is 60～95%; Diameter range 10 nanometers of rich N crystalline state alloy spherical particle～100 microns, percent by volume is 1～50%;
Immiscible alloy M-N is one of Al-Pb, Al-Bi, Al-In, Al-Cd, Ca-Gd, Ca-Na, Ce-V, Cu-Li, Cu-Nb, Cu-Co, Cu-Ta, Cu-Pb, Cu-Bi, Cu-W, Fe-In, Fe-Sn, Fe-Sr, Mg-Na, Ni-Pb, Ni-Ag, Sc-V, Sm-Ba, Ti-Gd, Y-V, Y-Cr alloy.
2, according to the described crystalline state alloy spherical particle/amorphous alloy base composite material of claim 1, it is characterized in that: other alloying elements of interpolation for one or more of the corresponding non-crystaline amorphous metal system of alloying element M composition, other alloying elements of interpolation and the enthalpy of mixing Δ H between the alloying element M
Mix -For negative, the liquid phase alloy of the rich M amorphous alloy matrix of miscible other alloying elements that add is 10～10
6Glass transition takes place under the K/s speed of cooling.
3, according to the described crystalline state alloy spherical particle/amorphous alloy base composite material of claim 1, it is characterized in that: alloying element M and N be awkward miscible alloy system under liquid state, immiscible alloy be between the constituent element enthalpy of mixing for just, repel mutually between the constituent element atom, immiscible alloy when liquid, other alloying elements and the alloying element N that add are immiscible under liquid state, and the sub-liquid phase of rich N crystalline state alloy spherical particle is 10～10
6Glass transition does not take place under the K/s speed of cooling.
4, according to the preparation method of the described crystalline state alloy spherical particle/amorphous alloy base composite material of claim 1, it is characterized in that, comprise the steps:
(1) has the metallurgy feature in liquid constituent element unmixing zone based on immiscible alloy, select and the optimization of Chemical Composition design, make alloy melt before glass transition takes place, liquid-liquid phase takes place earlier become, generate the matrix liquid phase L of rich M by alloy species
1Spherical liquid phase L with rich N
2, a spherical liquid phase L wherein
2Be distributed in another liquid phase L with the spherical droplets form
1In the matrix;
(2) subsequently fast in the process of cooling, the speed of cooling 10～10 of alloy melt
6K/s, matrix liquid phase L
1Glass transition takes place, spherical liquid phase L
2Spheroidal particle disperse after solidifying is distributed in the matrix, forms crystalline state alloy spherical particle/amorphous alloy base composite material.
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| US10428418B2 (en) * | 2016-11-11 | 2019-10-01 | City University Of Hong Kong | Metal material and a method for use in fabricating thereof |
| CN106544534B (en) * | 2017-01-13 | 2018-02-16 | 东北大学 | A kind of preparation method of the immiscible alloy with baseball composite construction particle |
| CN107130144B (en) * | 2017-06-01 | 2019-02-15 | 济南大学 | Homogeneous Al-Bi immiscible alloy of bulk and preparation method thereof |
| CN110257730B (en) * | 2018-03-12 | 2020-07-28 | 中国科学院物理研究所 | Cu-L i amorphous alloy and preparation method and application thereof |
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