CN108985004A - A kind of calculation method of ternary amorphous alloy maximum negative heat of mixing - Google Patents
A kind of calculation method of ternary amorphous alloy maximum negative heat of mixing Download PDFInfo
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- CN108985004A CN108985004A CN201810712019.7A CN201810712019A CN108985004A CN 108985004 A CN108985004 A CN 108985004A CN 201810712019 A CN201810712019 A CN 201810712019A CN 108985004 A CN108985004 A CN 108985004A
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 21
- 238000004364 calculation method Methods 0.000 title claims abstract description 17
- 239000004615 ingredient Substances 0.000 claims abstract description 13
- 229910001339 C alloy Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 11
- 229910002058 ternary alloy Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 5
- 229910002530 Cu-Y Inorganic materials 0.000 description 4
- 229910017767 Cu—Al Inorganic materials 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910017985 Cu—Zr Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
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Abstract
The invention discloses a kind of calculation methods of ternary amorphous alloy maximum negative heat of mixing.For any given ternary A-B-C alloy system, it is known that the ingredient of elements A then has AmB100‑xCx, wherein x < 100-m-x, and 0 < x < m, 0 < m < 100；If A-B enthalpy of mixing is Δ H1, B-C enthalpy of mixing is Δ H2, A-C enthalpy of mixing is Δ H3；For 1mol AmB100‑xCx, the enthalpy of mixing Δ H that is formed between x A, B and C atom1=x (Δ H1+ΔH2+ΔH3)；Enthalpy of mixing is Δ H2 between A atom a for remaining (m-x) and (100-m-2x) a B atom；Then Δ H=Δ H1+ Δ H2 is system maximum negative heat of mixing.The maximum negative heat of mixing of counting system of the present invention, the amorphous alloy component for designing maximum amorphous formation ability have important directive significance.
Description
Technical field
The invention belongs to amorphous alloy technical fields, more particularly, to a kind of ternary amorphous alloy maximum negative heat of mixing
Calculation method.
Background technique
The amorphous formation ability that the ingredient preparation of amorphous alloy is related to technological parameter, experimental situation and ingredient itself is big
The factors such as small.Under identical preparation process condition, if it is possible to the relatively large component system of amorphous formation ability is designed,
So the preparation process of amorphous is required to substantially reduce, there will be extreme influence for the popularization and application of bulk amorphous alloys.
The design of block amorphous alloy is typically all according to tri- principle of Inoue (three principle on well):
1) it is more than the multicomponent system of three kinds of constituent elements；
2) there have between basic component to be poor greater than 12% atomic size；
3) there is biggish negative heat of mixing between basic component.
There has been no the proposition of more specific method for the design of amorphous component is current, the calculating of amorphous enthalpy of mixing is by right
The DSC curve of alloy sample carries out area integral and obtains, and this method calculating is more complicated, and can only design alloying component
The enthalpy of mixing for calculating alloy system later only has verifying meaning to the design of amorphous alloy, and absolutely not designs ingredient
Directive significance.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, primary and foremost purpose of the present invention is to provide a kind of ternary non-
The calculation method of peritectic alloy maximum negative heat of mixing.It proposes in the base for determining ternary alloy three-partalloy element and one of component ratio known
On plinth, carry out system maximum negative heat of mixing calculating, thus for the strong design of alloy of amorphous formation ability provide theory according to
According to final design goes out the stronger amorphous alloy of amorphous formation ability, so that is be more easier prepares stronger amorphous alloy, is
The ingredient design of amorphous alloy provides certain theoretical foundation.
The purpose of the present invention is realized by following technical proposals:
A kind of calculation method of ternary amorphous alloy maximum negative heat of mixing, comprises the following specific steps that:
S1. any given ternary A-B-C alloy system, it is known that the ingredient of elements A then has AmB100-xCx, wherein x <
100-m-x, and 0 < x < m, 0 < m < 100；
S2. according to the mixing enthalpy between element, if the mixing enthalpy between A-B is Δ Hmix1, the mixing enthalpy between B-C is Δ
Hmix2, the mixing enthalpy between A-C is Δ Hmix3；
S3. perfect combination between hypothesis each element atom, then having total enthalpy of mixing H of system is the interatomic mutual knot of each element
The sum of close, for 1molAmB100-xCx, the enthalpy of mixing Δ H formed is combined between x A atom, x B atom and x C atom1=x
×(ΔHmix1+ΔHmix2+ΔHmix3)；
S4. the enthalpy of mixing formed between A atom a for remaining (m-x) and (100-m-2x) a B atom is Δ H2；
S5. step S3 and step S4 are added up into system maximum negative heat of mixing, i.e. Δ H=Δ H1+ Δ H2.
Preferably, if m-x >=100-m-2x, i.e. 100-2m≤x≤50-m/2 in step S4, then Δ H2=(100-m-2x)
×ΔHmix1=(100-m) × Δ Hmix1-2x×ΔHmix1, then Δ H=Δ H in step S51+ΔH2=(100-m) × Δ Hmix1+
x×(ΔHmix2+ΔHmix3-ΔHmix1)。
It is further preferable that if Δ Hmix1> Δ Hmix2+ΔHmix3When, when x takes maximum positive integer n1{(100-2m)≤n1≤
(50-m/2) }, molecular formula AmB100-m-n1Cn1When, gained Δ H=Δ H1+ΔH2The as maximum negative heat of mixing of system；If Δ
Hmix1< (Δ Hmix2+ΔHmix3) when, when x takes minimum positive integer n2{(100-2m)≤n2≤ (50-m/2) }, molecular formula is
AmB100-m-n2Cn2When, gained Δ H=Δ H1+ΔH2The as maximum negative heat of mixing of system.
Preferably, if m-x≤100-m-2x, i.e. x≤100-2m in step S4, then Δ H2=(m-x) × Δ Hmix1=m ×
ΔHmix1-x×ΔHmix1, then Δ H=Δ H in step S51+ΔH2=m × Δ Hmix1+x×(ΔHmix2+ΔHmix3)。
It is further preferable that if x takes maximum positive integer n3{n3≤(100-2m)(n3< 100-m-n3And n3< m) }, molecular formula
For AmB100-m-n3Cn3When, gained Δ H=Δ H1+ΔH2The as maximum negative heat of mixing of system.
Preferably, in ternary A-B-C alloy system described in step S1, A Zr, Fe, Ti or Cu, B Cu, Nb or Mg, C
For Al, Y or Co
The method of calculating ternary system enthalpy of mixing of the invention can determine in the case where known ternary alloy system
The Atomic radiuses difference of constituent element, therefore under conditions of not considering the influence of the other factors such as eutectic phasor, system need to be only determined again
Maximum negative heat of mixing, can be obtained this system.The method need to only know the content ratio of one of ingredient, can be to entire body
System carries out enthalpy of mixing calculating, finds out maximum enthalpy of mixing and then determines theoretical best amorphous formation ability ingredient.
Compared with prior art, the invention has the following advantages:
1. the calculation method of ternary amorphous alloy maximum negative heat of mixing provided by the invention, is determining ternary alloy three-partalloy element
And on the basis of one of component ratio known, the Optimal calculation of the maximum negative heat of mixing of system is carried out, is had simple, quick
The advantages that, for A-B-C ternary alloy system, it is known that the component content of elements A can carry out maximum negative mixing to system
The calculating of enthalpy, under the influence of ignoring other conditions, and then the best amorphous formation ability for learning system is closed at branch for amorphous
The ingredient exploitation of golden system provides certain theoretical foundation, causes so as to avoid a large number of experiments experiment of conventional alloys exploitation
Raw material waste.
2., according to the atom combination between element, calculating system the present invention is based on the mixing enthalpy between each element
Maximum negative heat of mixing.In the case where having determined that ternary alloy system has determined that component atoms radius size is poor, according to well
Upper three principle, it is only necessary to which the amorphous component of theoretical best Forming ability can be obtained by calculating maximum enthalpy of mixing.This hair
There is important guidance to anticipate for bright calculating maximum negative heat of mixing, the amorphous alloy component for designing maximum amorphous formation ability
Justice.
Detailed description of the invention
Fig. 1 is the calculating schematic diagram of the mixing enthalpy of Zr-Cu-Al alloy in embodiment 1.
Fig. 2 is the calculating schematic diagram of the mixing enthalpy of Mg-Cu-Y alloy in embodiment 2.
Fig. 3 is the calculating schematic diagram of the mixing enthalpy of Cu-Zr-Ti alloy in embodiment 3.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention.
Embodiment 1
A kind of calculation method of Zr-Cu-Al alloy maximum negative heat of mixing, the specific steps are as follows:
Known a certain ingredient (Zr46) content and other two kinds of element (Cu54-xAlx) the unknown Zr-Cu-Al ternary conjunction of content
Golden system carries out enthalpy of mixing calculating, molecular formula Zr46Cu54-xAlx；
Cu-Zr between known Zr (atomic radius 145pm)-Cu (atomic radius 117pm)-Al (atomic radius 118pm)
Enthalpy of mixing is -23kj/mol, and the enthalpy of mixing of Zr-Al is -44kj/mol, and the enthalpy of mixing between Cu-Al is -1kj/mol, is such as schemed
Shown in 1.
In the Zr of 1mol46Cu54-xAlxIn, what x Al atom was formed when combining respectively with x Zr atom, x Cu atom
Enthalpy of mixing H1=x × (- 44)+x × (- 1)=- 45xkj/mol；
There are two types of situations for the enthalpy of mixing that remaining (46-x) a Zr atom and (54-2x) a Cu atom generate:
(1) as (46-x) >=(54-2x), by 46-x > 0,54-2x > 0, when obtaining 8≤x < 27, H21=(54-2x) × (-
23)=- 1242+46x kj/mol, at this time Zr46Cu54-xAlxThe enthalpy of mixing negative peak H of system alloymax=H1+H21=-
1242-22x kj/mol, when x is maximum positive integer 26, molecular formula is Zr at this time46Cu28Al26, enthalpy of mixing has negative peak
Hmax=-1814kj/mol；
(2) as (46-x)≤(54-2x), by 46-x > 0, when 54-2x > 0, i.e. 0 < x≤8, H22=(46-x) × (- 23)
=-1058+23x kj/mol, at this time Zr46Cu54-xAlxThe enthalpy of mixing negative peak H of system alloymax=H1+H21=-1058-
45x kj/mol, when x is positive peak 8, enthalpy of mixing has negative peak Hmax=-1418kj/mol；Molecular formula is at this time
Zr46Cu46Al8。
For having determined that the Zr of Zr base content46Cu54-xAlxTernary alloy system, its molecule when Al element is relatively more
Formula is Zr46Cu28Al26When, it is -1814kj/mol that system, which has maximum negative enthalpy of mixing,；When Al element relative amount is less,
Molecular formula is Zr46Cu46Al8, the negative enthalpy of mixing of system maximum is -1418kj/mol.If not considering the other factors such as eutectic phasor
Under conditions of, then Zr46Cu28Al26In Zr46Cu54-xAlxIn ternary alloy system have maximum amorphous formation ability alloy at
Point.
Embodiment 2
A kind of calculation method of Mg-Cu-Y alloy maximum negative heat of mixing, the specific steps are as follows:
Known a certain ingredient (Zr65) content and other two kinds of element (Cu35-xAlx) the unknown Mg-Cu-Y ternary conjunction of content
Golden system carries out enthalpy of mixing calculating, molecular formula Mg65Cu35-xYx；
Cu-Mg's is mixed between known Mg (atomic radius 136pm)-Cu (atomic radius 117pm)-Y (atomic radius 162pm)
Closing enthalpy is -3kj/mol, and the enthalpy of mixing of Mg-Al is -38kj/mol, and the enthalpy of mixing between Cu-Y is -22kj/mol, such as Fig. 2 institute
Show.
In the Mg of 1mol65Cu35-xYxIn, x Y atom forms mixed when combining respectively with x Mg atom, x Cu atom
Close enthalpy H1=x × (- 38)+x × (- 22)=- 60xkj/mol；
The enthalpy of mixing situation that remaining (65-x) a Mg atom and (35-2x) a Cu atom generate is as follows:
It is set up because (65-x) >=(35-2x) is permanent, by 65-x > 0,35-2x > 0, when obtaining 0 < x≤17, H21=(35-2x) ×
(- 3)=- 105+6x kj/mol, at this time Mg65Cu35-xYxThe enthalpy of mixing negative peak H of system alloymax=H1+H2=-105-
54x kj/mol, when x is maximum positive integer 17, molecular formula is Mg at this time65Cu18Y17, enthalpy of mixing has negative peak Hmax=-
1023kj/mol；
For having determined that the Mg of Mg base content65Cu35-xYxTernary alloy system, when its molecular formula is Mg65Cu18Y17When, body
It is -1023kj/mol that, which there is maximum negative enthalpy of mixing in system,.If under conditions of not considering the other factors such as eutectic phasor,
Mg65Cu18Y17 areIn Mg65Cu35-xYxWith the alloying component of maximum amorphous formation ability in ternary alloy system.
Embodiment 3
A kind of calculation method of Cu-Zr-Ti alloy maximum negative heat of mixing, the specific steps are as follows:
Known a certain ingredient (Cu60) content and other two kinds of element (Zr40-xTix) the unknown Cu-Zr-Ti ternary conjunction of content
Golden system carries out enthalpy of mixing calculating, molecular formula Cu60Zr40-xTix；
Cu-Zr between known Cu (atomic radius 117pm)-Zr (atomic radius 145pm)-Ti (atomic radius 132pm)
Enthalpy of mixing is -23kj/mol, and the enthalpy of mixing of Zr-Ti is 0kj/mol, and the enthalpy of mixing between Cu-Ti is -9kj/mol, such as Fig. 3
Shown in.
In the Cu of 1mol60Zr40-xTixIn, what x Ti atom was formed when combining respectively with x Zr atom, x Cu atom
Enthalpy of mixing H1=x × (- 9)=- 9xkj/mol；
The enthalpy of mixing situation that remaining (60-x) a Cu atom and (40-2x) a Zr atom generate is as follows:
Because of (60-x) >=(40-2x), by 60-x > 0,40-2x > 0, when obtaining 0 < x < 20, H2=(40-2x) × (- 23)
=-920+46x kj/mol, at this time Cu60Zr40-xTixThe enthalpy of mixing negative peak H of system alloymax=H1+H2=-920+37x
Kj/mol, when x is minimum positive integer 1, molecular formula is Cu at this time60Zr39Ti1, enthalpy of mixing has negative peak Hmax=-920kj/
mol；
For having determined that the Cu of Zr base content60Zr40-xTixTernary alloy system, when its molecular formula is Cu60Zr39Ti1When,
It is -920kj/mol that system, which has maximum negative enthalpy of mixing,.If under conditions of not considering the other factors such as eutectic phasor,
Cu60Zr39Ti1For in Cu60Zr40-xTixWith the alloying component of maximum amorphous formation ability in ternary alloy system.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of calculation method of ternary amorphous alloy maximum negative heat of mixing, which is characterized in that comprise the following specific steps that:
S1. any given ternary A-B-C alloy system, it is known that the ingredient of elements A then has AmB100-xCx, wherein x < 100-m-
X, and 0 < x < m, 0 < m < 100；
S2. according to the mixing enthalpy between element, if the mixing enthalpy between A-B is Δ Hmix1, the mixing enthalpy between B-C is Δ Hmix2,
Mixing enthalpy between A-C is Δ Hmix3；
S3. perfect combination between hypothesis each element atom, then the total enthalpy of mixing H for having system, which is that each element is interatomic, be combined with each other it
With for 1mol AmB100-xCx, the enthalpy of mixing Δ H formed is combined between x A atom, x B atom and x C atom1=x ×
(ΔHmix1+ΔHmix2+ΔHmix3)；
S4. the enthalpy of mixing formed between A atom a for remaining (m-x) and (100-m-2x) a B atom is Δ H2；
S5. step S3 and step S4 are added up into system maximum negative heat of mixing, i.e. Δ H=Δ H1+ Δ H2.
2. the calculation method of ternary amorphous alloy maximum negative heat of mixing according to claim 1, which is characterized in that step S4
M-x >=100-m-2x in if, i.e. 100-2m≤x≤50-m/2, then Δ H2=(100-m-2x) × Δ Hmix1=(100-m) × Δ
Hmix1-2x×ΔHmix1, then Δ H=Δ H in step S51+ΔH2=(100-m) × Δ Hmix1+x×(ΔHmix2+ΔHmix3-Δ
Hmix1)。
3. the calculation method of ternary amorphous alloy maximum negative heat of mixing according to claim 2, which is characterized in that if Δ
Hmix1> Δ Hmix2+ΔHmix3When, when x takes maximum positive integer n1{(100-2m)≤n1≤ (50-m/2) }, molecular formula is
AmB100-m-n1Cn1When, gained Δ H=Δ H1+ΔH2The as maximum negative heat of mixing of system；If Δ Hmix1< (Δ Hmix2+Δ
Hmix3) when, when x takes minimum positive integer n2{(100-2m)≤n2≤ (50-m/2) }, molecular formula AmB100-m-n2Cn2When, gained Δ H
=Δ H1+ΔH2The as maximum negative heat of mixing of system.
4. the calculation method of ternary amorphous alloy maximum negative heat of mixing according to claim 1, which is characterized in that step S4
M-x≤100-m-2x in if, i.e. x≤100-2m, then Δ H2=(m-x) × Δ Hmix1=m × Δ Hmix1-x×ΔHmix1, then walk
Δ H=Δ H in rapid S51+ΔH2=m × Δ Hmix1+x×(ΔHmix2+ΔHmix3)。
5. the calculation method of ternary amorphous alloy maximum negative heat of mixing according to claim 4, which is characterized in that if x takes
Maximum positive integer n3{n3≤(100-2m)(n3< 100-m-n3And n3< m) }, molecular formula AmB100-m-n3Cn3When, gained Δ H=
ΔH1+ΔH2The as maximum negative heat of mixing of system.
6. the calculation method of ternary amorphous alloy maximum negative heat of mixing according to claim 1, which is characterized in that step S1
Described in ternary A-B-C alloy system, A Zr, Fe, Ti or Cu, B Cu, Nb or Mg, C Al, Y or Co.
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| CN102808150A (en) * | 2012-09-12 | 2012-12-05 | 大连理工大学 | Cu-Ni-Nb ternary alloy film with low resistivity and high chemical inertia and preparation process thereof |
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| CN102808150A (en) * | 2012-09-12 | 2012-12-05 | 大连理工大学 | Cu-Ni-Nb ternary alloy film with low resistivity and high chemical inertia and preparation process thereof |
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| Title |
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| 陶鹏等: "Fe97-xNb3Bx铁基非晶合金的热学与磁学性能研究", 《西安工业大学学报》 * |
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