The prediction of solid solubility of alloys: developments and applications of

Hume-Rotherys rules
Y.M. Zhang

!. R.". #vans
$
%. Yang
a
1. Centre for Materials Research and School of Engineering and Materials Science
Queen Mary, University of London
Mile End Road
London E1 4NS
. !e"art#ent of Che#istry,
University College London,
$ %ordon Street,
London &C1' $(), U*
a
(uthor to +ho# corres"ondence should ,e addressed. E#ail- S.yang./#ul.ac.u0,
1
&bstract:
1n the 12$s, 'u#e3Rothery hel"ed to #a0e the art of #etallurgy into a science ,y
the discovery of rules for the "rediction of solu,ility in alloys. 4heir si#"licity and
generality #ade the# ,eco#e one of the #ost i#"ortant rules in #aterials science. 1n
the fe+ decades after 'u#e3Rothery5s discovery, #any researchers have tried to
#a0e 6corrections7 to '3R rules ai#ing to #a0e the# +or0 ,etter in general alloy
syste#s. 4hose researches included e8"lanations of the rules using /uantu# and
electron theories and ne+ co#,inations of the factors to give ,etter #a""ing. 1n this
"a"er, +e revie+ #ost of these contri,utions and introduce recent "rogress in
solu,ility "rediction using artificial neural net+or0s.
*ey+ords- solu,ility, alloys, 'u#e3Rothery rules, electronegativity, artificial neural
net+or0.

.' (ntroduction
4he #ost +idely acce"ted vie+ of scientific #ethod is ,ased on the creative
e#ergence of hy"otheses or con9ectures :1; +hich gradually ,eco#e +ell3trenched in
the for# of esta,lished theories as #ore su""orting e8"eri#ental evidence is sought
and found. ( contrasting #odel for scientific discovery is attri,uted to <rancis =acon
>1?@131@@A in +hich large a#ounts of data are first collected, asse#,led into ta,les,
surveyed and fro# +hich theories are devised :;. ( central de,ate in the history and
"hiloso"hy of science focuses on these contrasting e8"lanations of scientific #ethod
and is concisely articulated ,y %illies in his analysis of artificial intelligence :B;.
'u#e3Rothery5s rules, occu"ying a central s"ace at the heart of #etallurgy, are in the
=aconian tradition. 1n the 12$5s, after surveying the availa,le solu,ility data, 'u#e3
Rothery distinguished the factors that influence co#"ound for#ation and control
alloying ,ehaviour. 4here e8ists a connection ,et+een solu,ility, ato#ic siCe, crystal
structure and a "articular concentration of valence electrons in an alloy :4, ?;. 'u#e3
Rothery added other ideas, develo"ing conce"ts +hich are no+ 0no+n collectively as
'u#e3Rothery5s rules :@3D;. <ro# these and his other +or0s, 'u#e3Rothery ,eca#e
the "erson +hose +or0 can 9ustifia,ly ,e lauded for #a0ing the art of #etallurgy into
a science :2;.
<ollo+ing this hugely significant +or0 ,y 'u#e3Rothery and his colleagues on the
"rediction of solid solu,ility in alloys, #any researchers, such as !ar0en and %urry
:1$;, Cheli0o+s0y :11;, (lonso and Si#oCar :1;, (lonso et al. :1B; and Ehang and
Liao :14, 1?; all contri,uted in different +ays to the "rediction of solid solu,ility in
ter#s of a solu,leFinsolu,le criterion. 4here are already detailed revie+s of 'u#e3
Rothery5s rules, such as the +or0 ,y Massals0i and *ing :1@;, Massals0i and
B
MiCutani :1G;, Massals0i :4, 1D; and as descri,ed in ,iogra"hical s0etches a,out
'u#e3Rothery :12;. Researches on '3R rules ,losso#ed in the 12B$s312D$s ,ut the
"rediction of solu,ility +as gradually su"erseded ,y calculation of "hase diagra#s
>C(LH'(!A. 'o+ever, the si#"licity and generality of '3R rules still #a0e the#
one of the #ost i#"ortant cornerstones in #aterials science. &atson and &einert in
$$$ :$; #entioned #ost of these rules are still useful today as in 'u#e3Rothery5s
ti#e, and discussed the a""lications to the transition and no,le alloys, ,oth +ith each
other and +ith #ain grou" ele#ents. HarthI :1; discussed a""lication of D3N and
valence electron rules for the Eintl "hases >+hich are defined as 6se#i#etallic or even
#etallic co#"ounds +here the underlying ionic3covalent ,onds "lay such an
i#"ortant role that che#ically ,ased valence rules can ,e used to account for
stoichio#etry and o,served structural features7A and their e8tension. Recently these
rules have also ,een used in nanocrystal gro+th and co#"ound for#ing tendency :;
as +ell as ther#odyna#ically sta,ility of ordered structures in 111FJ se#iconductor
alloys :B;. 1n this revie+, the authors ai# to address so#e recent "rogress on the
develo"#ent and a""lication of '3R rules.
(s cautioned ,y Hettifor :12;, ,ecause different rules +ere e8"ressed or stressed ,y
'u#e3Rothery at different ti#es, it is so#eti#es difficult to define +hat constitutes
K'u#e3Rothery Rules5 and this confusion is e8tant. 4here is general agree#ent that,
in order of i#"ortance, the ato#ic siCe factor is first, follo+ed ,y the electro3
negativity effect. 4he i#"ortance of the electron concentration >eFa ratioA in
deter#ining solid solu,ility ,oundaries is recognised in so#e cases ,ut other factors
are rarely discussed in sufficient detail. Surveying #etallurgical and "hysical science
4
"u,lications in general, different sources e8"ress 'u#e3Rothery5s ideas using ter#s
such as- effects, "rinci"les, factors or "ara#eters :4;.
$.' #arly )ormation and Revision of Hume-Rotherys Rules
1n 12?, after ta0ing his Hh! under Sir 'arold Car"enter at the Royal School of
Mines, 'u#e3Rothery returned to L8ford and +or0ed on inter#etallic co#"ounds,
#etallogra"hy and che#istry, e8tending his ideas on the for#ation of co#"ounds.
'e e8a#ined "hase diagra#s of the no,le and related #etals >i.e. Cu, (g and (uA,
es"ecially those alloyed +ith the =3su,grou" ele#ents >these include Li, =e, =, C, N,
L, <, Na, Mg, (l, Si, H, S, Cl, En, %a, %e, (s, Se, =r, Cd, 1n, Sn, S,, 4e, 1, 'g, 4l,
H,, =iA. 4his field ,eca#e fertile in the "eriod of 12?312@ and at the end of 12?,
'u#e3Rothery su,#itted his first and classical "a"er on the to"ic of co#"ound
for#ation in several alloy syste#sM this "a"er +as "u,lished in 12@ :?;. 1n it, 'u#e3
Rothery "redict the N "hase of Cu
B
(l +ould have the ,cc structure ,ecause it satisfied
an electron "er ato# ratio of BF, and this +as confir#ed one #onth later through
e8"eri#ent ,y &estgren and Hhrag#In :4;.
1t should ,e #entioned that the electron "er ato# ratio BF, "ro#inent at that ti#e in
'u#e3Rothery5s ideas, can ,e e8"lained fro# the electron3lattice theory of
Linde#ann +hich "ro#oted 'u#e3Rothery5s conce"t of electron concentration as a
factor influencing structural sta,ility. 'o+ever, in 12@@, 'u#e3Rothery +rote- 64he
electron3lattice theory is no+ ad#itted to ,e an incorrect a""roach, and it re#ains an
e8a#"le of the +ay in +hich a theory #ay ,e of value, even though it turns out to ,e
/uite +rong7 :?;.
?
1n the 12B$s, 'u#e3Rothery shifted his attention to characterisation of ato#ic siCe ,y
nearest neigh,our distance instead of volu#e :@;. 4+o of the 'u#e3Rothery rules
controlling solid solu,ility +ere discovered- 1A the first 'u#e3Rothery rule, the
ato#ic siCe factor, said that if the ato#ic dia#eters of the solvent and solute differ ,y
#ore than a,out 1431?O then the "ri#ary solid solu,ility +ill ,e very restrictedM A
the second rule e#"hasised the i#"ortance of the electron concentration >or electron
"er ato# ratioA in deter#ining the "hase ,oundary. =oth of these rules are "resented
in his classical "a"er in 12B4 :@;.
(lthough 'u#e3Rothery at that ti#e had found t+o i#"ortant guidelines +hich
decided the for#ation of "ri#ary solid solutions, he +as unclear ho+ to classify
inter#etallic co#"ounds. 1n 12BG, after studied the silver rich anti#ony3silver alloy
syste# +ith Reynolds :G;, 'u#e3Rothery ,eca#e a+are of a third factor restricting
solid solu,ility, that is, electroche#ical factorM #a8i#u# solid solu,ility reduced as
the electronegativity difference ,et+een solute and solvent increased ,ecause of the
co#"etition to for# inter#etallic co#"ounds.
4he relative valence rule +as #entioned in the 12B4 "a"er, and the i#"ortance of this
rule +as stressed ,y 'u#e3Rothery in early editions of his fa#ous ,oo0 The
Structure of Metals and Alloys :G;. 'o+ever, in his later versions of this ,oo0, it is
stated K#ore detailed e8a#ination has not confir#ed this and, in its general for#, the
su""osed "rinci"le #ust no+ ,e discarded5 :D, 2;.

*.' )urther development and application of Hume-Rotherys Rules
@
4he develo"#ent of 'u#e3Rothery5s Rules can ,e classified into t+o categories- 4he
first is the develo"#ent +ithin each rule, and the second is the develo"#ent of
ana#or"hoses or alternatives of these rules as a +hole in order to get #ore "o+erful
and "recise "redictions. 1n the first category, researchers, 1A "rovided e8"lanations of
s"ecific rule>sA fro# ele#entary electron theory, A "ointed out the +ea0ness and
deficiency of individual rules. 1n the second category, researchers have atte#"ted to
e8tend the rule>sA or itsFtheir alternatives to +ider a""lications. 1n +hat follo+s, the
discussion "rogresses along these t+o "aths.
*. +evelopment and application of each rule
*.. &tomic %i,e )actor
4he ato#ic siCe factor rule is usually "resented in the follo+ing +ay :@;- 6if the
ato#ic dia#eters of the solute and solvent differ ,y #ore than 14O, the solu,ility is
li0ely to ,e restricted ,ecause the lattice distortion is too great for su,stitutional
solu,ility.7 &hen the siCe factor is unfavoura,le, the "ri#ary solid solu,ility +ill ,e
restrictedM +hen the siCe factor is favoura,le, other factors li#it the e8tent of solid
solu,ility and it is of secondary i#"ortance. &a,er et al. :B$; a""lied the siCe factor
alone to 14B ter#inal solid solutions and +ithin 2$.B1O >??2F@12A of the syste#s
+here lo+ solid solu,ility +as "redicted, lo+ solid solu,ility +as indeed o,served.
Ln the other hand, it +as less easy to "redict extensive solid solu,ility +hen there +as
a s#all siCe differenceM it achieved only a ?$ O >4$BFD$4A success rate. 4he siCe factor
rule has ,een e8"lained ,y using ele#entary electron theory. 1t can ,e sho+n that :B13
B4;, if a #isfitting solute ato# is regarded as an elastic s"here +hich is then
co#"ressed or e8"anded into a hole of the +rong siCe in the solute lattice, +hich can
G
,e treated as an isotro"ic elastic continuu#, the ensuing total strain energy E in ,oth
the #atri8 and solute can ,e esti#ated as
B
$
D r E
, >E/uation 1A
+here P is the shear #odulus and r
$
and >1QRAr
$
are the unstrained radii of the solvent
and solute ato#s. 4a0ing R as $.14 >as the siCe factor rule declaresA or $.1?, and
B
$
r
S$.G eJ, this gives
T k E
B
4
at 1$$$ *. !ar0en and %urry :1$; "roved that at
te#"erature 4, the "ri#ary solid solu,ility +ould ,e restricted to ,elo+ a,out 1 at.O
+hen the energy of solution e8ceeds 40
=
4 "er ato#, +here 0
=
is =oltC#ann5s
constant. (lthough elastic theory cannot ,e a""lied strictly at the ato#ic level, this
gives a si#"le e8"lanation of 'u#e3Rothery5s siCe factor rule.
Mott :BB; "rovided a /uantu# #echanical ,asis for elastic theory ,ased the &igner3
SeitC +ave function T
$
>rA, for an electron in the lo+est state in a &igner3SeitC cell.
4he +avefunction for an electron in the alloy can ,e e8"ressed a""ro8i#ately as T>rA
S u >rA e8" >ik U rA, +ith u >rA having the for#s of an ( ato# or a = ato# &igner3SeitC
+avefunction T
$
>rA inside the &igner3SeitC cells of ( or = ato#s >if ( and = are of
the sa#e valencyA in the alloy, +here r is the vectorial "osition of the electron and k is
the +ave3vector. <or a single solute ato# = in a dilute solution, a difference in
&igner3SeitC radius for solute ato#, r
=,
and solvent ato#, r
(
, #eans the +ave function
T
$
for solute ato# #ust ,e found fro# an inter#ediate radius rM r
(
V r V r
=.
4his is a
si#ilar "ro,le# to finding the ,ul0 #odulus of = fro# &igner3SeitC theory and the
e8"ansion of the hole in the solvent (, fro# r
(
to r, is e/uivalent to a "ro,le# in the
elasticity of #etal (.
D
4he validity of the siCe factor has ,een de,ated since the rule +as "ro"osed. 'u#e3
Rothery et al. the#selves "ointed out :@; that the e8act 6ato#ic dia#eter7 of an
ele#ent is al+ays difficult to define. 4hey defined the ato#ic dia#eter as given ,y
the nearest3neigh,our distance in a crystal of the "ure #etal. 'o+ever, this dia#eter
cannot necessarily ,e transferred to the alloy ,ecause 1A the Kradius5 of an ato# is
"ro,a,ly affected ,y coordination nu#,er. E8ce"t for the heavy ele#ents, ele#ents
of the = su,3grou"s tend to crystalliCe +ith coordination nu#,er D3N, +here N is the
grou" to +hich the ele#ent ,elongs. 4his is due to the "artly covalent nature of the
forces in these crystals and, e8ce"t in %rou" 1J =, results in the ato#s having t+o
sets of neigh,ours at different distances in the crystal. A 1n so#e structures there are
great variations in the closest distance ,et+een "airs of ato#s at their closest distance
of a""roach, de"ending on the "osition and direction in the lattice. BA Ln for#ing a
solid solution, the KsiCes5 of individual ato#s #ay change according to the nature and
degree of local dis"lace#ents. 1n the case of anisotro"ic or co#"le8 structures or
+here the coordination nu#,ers are lo+, the closest distance of a""roach does not
ade/uately e8"ress the siCe of the ato# +hen in solid solution :1D;. <urther#ore,
ato#ic s"acing increases or decreases as the co#"osition changes and so differences
a""ear ,et+een the lattice s"acing in alloys and the esti#ated ato#ic siCes.
4here are so#e atte#"ts to derive the ato#ic siCe, such as e8tra"olating the siCe
variance trend of an ele#ent in the alloy to+ards the "ure ele#ent to give a
hy"othetical siCe :B?;. Massals0i and *ing :1@; "ointed out that in finding the ato#ic
siCe factor, it is usually the volu#e "er ato# that #atters, not the distance ,et+een
nearest neigh,ours, so they used the change in volu#e "er ato# to o,tain hy"othetical
di#ensions.
2
4he ato#ic di#ensions can ,e calculated ,y using "seudo"otential theory, such as the
+or0 done ,y 'ayes et al. :B@; on Li3Mg, 1nglesfield :BG3B2; on 'g, Cd and Mg
alloys, 'ayes and Woung :4$; on al0ali alloys, Stroud and (shcroft :41; for Cu3(l,
Li3Mg and Cu3En, Meyer et al. :4344; on analyCing the diffusion ther#o"o+ers of
dilute al0ali #etal alloys, on calculating the lattice s"acings and co#"ressi,ilities of
non3transition ele#ent solids and for analyCing residual resistivities in silver and gold
and Singh and Woung :4?; on heats of solution at infinite dilution. 4hey can also ,e
o,tained fro# the free3electron #odel develo"ed ,y =roo0s :4@; and have ,een used
,y Magnaterra and MeCCetti :4G, 4D;.
4he actual individual ato#ic siCes can also ,e esti#ated fro# static distortions in a
solid solution ,y #odulation in diffuse X3ray scattering :42, ?$; or fro# +ea0ening of
the interference #a8i#a analogous to ther#al effects :?13?4;.
<ro# the analyses cited a,ove, and as Cottrell :??; suggested, the conce"t of a
characteristic siCe, +hich suggests hard s"heres ,utted together is dou,tful and
allocating a single ato#ic dia#eter for each ele#ent, inde"endent of its environ#ent,
and valences of solvent and solute is too si#"listic an a""roach :2;. (t "resent, the
i#"ortance of the siCe factor of course e8tends far ,eyond "ri#ary solu,ility. Many
inter#etallic co#"ounds o+e their e8istence to siCe3factor effects.
*..$ Relative -alence )actor
(n early discovery ,y 'u#e3Rothery +as that a #etal of lo+er valence is #ore li0ely
to dissolve one of higher valence than vice versa. 'o+ever, #ore e8tensive
1$
investigation has not confir#ed the generality of this rule. (n e8a#"le is that
#onovalent silver can dissolve a,out $O alu#iniu# ,ut trivalent alu#iniu#
dissolves a,out 4O silver. 'o+ever, for high valence, covalently ,onded
co#"onents, the relative valence factor a""lies +ell. <or e8a#"le, co""er dissolves
a,out 11O of silicon ,ut silicon dissolves negligi,le co""er :??;. 4his rule see#s to
,e valid only +hen #onovalent #etals co""er, silver or gold are alloyed +ith the =3
su,grou" ele#ents of the Heriodic 4a,le +hich have higher valences. 4his is
variously attri,uted to the "artial electron filling of the =rillouin Cones in no,le
#etals, the interaction of <er#i surfaces and =rillouin Cones in =3su,grou" ele#ents
:1D; and long3range charge oscillations around the i#"urity ato#s :?@;. %schneidner
:?G; i#"lies that the relative valence effect is li#ited in a""lica,ilityM +hen t+o high
valence ele#ents are alloyed it is not al+ays "ossi,le to "redict +hich +ill for# the
#ore e8tensive solid solution +ith the other.
=esides, the valencies of transition #etals are varia,le and co#"le8, as analysed ,y
'u#e3Rothery et al. :?D; and Coc0ayne and Raynor :?2;. Cottrell5s ,oo0 :??; "oints
out that due to the valency co#"lication caused ,y "artly filled d or,itals, the
transition #etal alloys generally do not follo+ the rule. %schneidner :?G; revised the
relative valence rule to suggest that the solu,ility +ill ,e lo+ if a #etal in +hich d
or,itals strongly influence the valence ,ehaviour is alloyed +ith a Ksp #etal5. 4he
solu,ility is li0ely to ,e higher in the d #etal than the reverse.
*..* #lectronegativity factor
4he scale for electronegativity as given ,y Mulli0an is ,ased on the e/uation-
( ) A I +

, >E/uation A
11
+here I is the ioniCation energy, A is electron affinity, and Y is Mulli0an
electronegativity. !ividing ,y .D, gives a""ro8i#ately Hauling5s e#"irical scale.
&atson and =ennett :@$; "oint out that in the case of transition #etals, the "artly
filled d states at energies near the <er#i energy influence electronegativity. 4hey
"roduced an electronegativity scale for transition #etals, +hich #atches Hauling5s
scale, and could ,e scaled ,y .D to ,ring it to Mulli0an5s scale.
(s discussed ,y 'u#e3Rothery :?@;, sta,le inter#etallic co#"ounds are "rone to
for# as the #ore electronegative is the solute and the #ore electro"ositive is the
solvent #etal, or vice versa. !ue to the lo+er free energy that can ,e o,tained +hen
the syste# ado"ts a #i8ture of solid solution and co#"ound, solute ato# "artition to
for# the sta,le co#"ound rather than to enter solid solutions.
<urther, as stated ,y Hearson :@1;, in so#e ,inary alloy syste#s, if one co#"onent is
very electro"ositive relative to the other, there +ould ,e a strong tendency for the# to
for# co#"ounds of considera,le sta,ility in +hich valence rules are satisfied. 4his is
the strongest effect in deter#ining the constitution of alloys, +hich do#inates all
other effects.
Recently, Li and Xue :@;, on the ,asis of an effective ionic "otential that is defined
in ter#s of ionisation energy and ionic radius, calculated the electronegativities of D
ele#ents in different valence states and +ith the #ost co##on coordination nu#,ers,
and "ointed out that Kalthough electronegativity is often treated as an invariant
"ro"erty of an ato#, as in Hauling5s scale, it actually de"ends on the che#ical
environ#ent of the ato#, e.g. valence state, coordination nu#,er and s"in state5.
1
1n addition to these efforts to e8"lain each rule using /uantu# or electronic theory,
another category of develo"#ent has ,een to #a" the solu,leFinsolu,le syste#s in a
t+o di#ensional diagra#.
*.$ Mapping and derivatives of Hume-Rotherys Rules
(lthough e8tensive researches have ,een done to +or0 out the theory ,ehind the '3R
rules, it +ould ,e very useful if the solu,ility of the #aterials can ,e #a""ed
diagra##atically on a Cartesian syste#. So researchers can si#"ly calculate the
coordinate of the ele#ent to "redict the solu,ility using such a diagra#. 4his
direction started fro# !ar0en and %urry :1$;, follo+ed ,y %schneidner :?G;,
Cheli0o+s0y :11;, (lonso et al. :1, 1B;, and Ehang :14, 1?; a#ong others.
*.$. +ar.en-"urry method
1n 12?B, !ar0en and %urry :1$; "ro"osed a diagra##atic #ethod to descri,e the
solid solu,ility of fifty alloy syste#s >!% #ethodA. 4hey used the siCe factor as
a,scissa and electroche#ical factor >electronegativityA as ordinate to "lot solu,ilities
of each alloy syste# and then dra+ an elli"se >r
solvent
Z 1?O as #inor a8is, Y
solvent
Z $.4
as "rolate a8is, +here r
solvent
and Y
solvent
are radius and electronegativity of solvent
res"ectivelyA to se"arate the solu,le ele#ents fro# the insolu,le ele#ents. 4he result
is sho+n in <igure 1. 4he solu,ility is characteriCed /ualitatively as 6e8tensive7 or
6li#ited7, inside the elli"se or outside the elli"se, res"ectively. 4hey a""lied this
#ethod to #agnesiu#, alu#iniu# and silver alloy syste#s. 4he electroche#ical
factor +as ta0en as the difference of $.4 >[ Y
solvent
3 Y
solute
[ V$.4A. 4his #ethod +or0s +ell
for the #agnesiu# alloy syste#s ,ut not for the silver syste#s. 4he reason for
1B
unsuccessful classification in silver syste#s +as, at that ti#e, attri,uted to the use of
una""roved electronegativity values of silver ,ut %schneidner :?G; argued that even if
a""roved electronegativity values for silver +ere used, the classification +ould still ,e
"oor.
&a,er et al. :B$; e8a#ined the universality of the 'u#e3Rothery siCe rule and the
!% #ethod for "redicting solid solu,ilities. (fter analyCed 14?? ,inary alloy
syste#s, they confir#ed 'u#e3Rothery5s siCe factor and sho+ed that the
electronegativity is an i#"ortant consideration in the for#ation of solid solutions.
>insert figure 1 hereA
1n 12D$, %schneidner :?G; again a""lied the !% #ethod to create a solu,leFinsolu,le
classification ,y introducing the effect of crystal structure >electronic3crystal structure
!ar0en3%urry #ethod, ECS!%A. <ro# that, he for#ulated four rules- 1A 1n the case
that ,oth solvent and solute are d3ele#ents, only the siCe rule governs the e8tent of the
solid solution region. 4hey argue that for the co##on crystal structures, f.c.c, ,.c.c.
and h.c."., there are #any lo+ directionality ,onds and to a first a""ro8i#ation, it is
unnecessary to use the crystal structure criterion. A. 1n cases +here the solvent is a d3
ele#ent and the solute is an sp3ele#ent, the crystal structure criterion is a""lied first
and if the crystal structures are the sa#e then the siCe rule is a""lied to "redict
+hether or not e8tensive or li#ited solu,ility is e8"ectedM BA. 1n the case +here ,oth
solvent and solute are sp3ele#ents, the crystal structure criterion is a""lied first, and if
this factor is favoura,le then the siCe rule is a""lied to "redict the e8tent of solid
solution. 1f the crystal structure criterion is not satisfied, then little or no solu,ility is
14
e8"ectedM 4A. 1n cases +here the solvent is an sp3ele#ent and solute is a d3ele#ent, no
solid solutions are "redicted to for#, regardless of either the crystal structure or siCe
factors. (""lying the ECS!% rules to ten solvents >Mg, (l, <e, %e, Hd, (g, Cd, La,
& and H,A, it is found the i#"rove#ent in the "rediction of e8tensive solid solu,ility
co#"ared +ith !% #ethod.
Recently, %schneidner and Jer0ade :@B; "resented the co#"lete details of their se#i3
e#"irical a""roach >called electronic and crystal structure, siCe #odel, ECS

A, and
"ointed out that their #ethod should also ,e /uite good at "redicting the e8tent of
another ele#ent in a ,inary co#"ound. 1n co#"ounds, iA the co#"ati,ility of the
crystal structure of the solute +ith either or ,oth of the co#"onents of the
inter#etallic "hase is regarded as a critical factorM iiA the valence of the solute
co#"ared +ith the co#"onents is also decisive iiiA if the a,ove t+o criteria are
favoura,le, then ato#ic siCe factor +ould ,e the final decisive issue and ,ecause of
the less elastic nature of co#"ounds co#"ared +ith ele#ental #etals, a Z1$O
li#itation on ato#ic siCe should ,e a""lied.
*.$.$ /heli.o0s.ys method
1n the 12G$s, t+o events occurred that led :11; to the vie+ that so#e of the ,arriers to
understanding solid solu,ility in inter#etallic alloys could ,e re#oved. Lne +as that
Miede#a and colla,orators "redicted and classified heats of for#ation for regular
inter#etallic alloys +hich is "redo#inantly deter#ined ,y the electronegativity
difference >
\

A and the difference in electron density at the ,oundary of the
&igner3SeitC cell >
WS
n
A of "ure #etals :@43@D;. 4he other +as that *auf#ann and
co3+or0ers develo"ed ion3i#"lantation techni/ues and conducted ion3i#"lantation to
1?
"rovide a +ide range of ne+ and uni/ue #etasta,le alloy syste#s, uno,taina,le ,y
conventional #etallurgical "rocedures :@23G1; +hich led to su,se/uent efforts to
study solid solu,ility in alloys :G3G?;.
1n 12G2, Cheli0o+s0y introduced a gra"hical "rocedure si#ilar to the !ar0en3%urry
#ethod to analyse solid solu,ility in the case of divalent hosts. 1n his +or0, a different
"air of coordinates +ere introduced- the electron density at the ,oundary of ,ul0
ato#ic cells,
WS
n
, and the electronegativity
\

. (s #entioned ,efore, these t+o

coordinates are the funda#ental "ara#eters in a successful se#i3e#"irical theory of
heats of alloy for#ation develo"ed ,y Miede#a and co3+or0ers :@43@D;. 1n his ne+
0ind of "lot, Cheli0o+s0y +as a,le to give #ore relia,le "redictions. (n e8a#"le of
Cheli0o+s0y "lots and a co#"arison +ith !ar0en3%urry "lots are sho+n in <igure .
Lther results can ,e found in Cheli0o+s0y5s "a"er :11;.
>insert figure hereA
<ro# <igure >,A and other results in his "a"er, #ost of the #etals +hich are solu,le
in a given host are ,ounded ,y the elli"se and this is so even if the "recise location
varies fro# host to host. 4his higher accuracy of "rediction can ,e inter"reted ,y the
relation ,et+een the Miede#a coordinates and #ore ele#entary descri"tions of alloy
for#ation, as develo"ed ,y others :G@32$;. Recently, the Miede#a "ara#eters +ere
used to "redict the for#ation of /uasicrystals :21, 2;.
Co#"aring Cheli0o+s0y5s #ethod +ith !ar0en3%urry5s, ,oth have a coordinate in
co##on ] the electronegativity. 1n !ar0en3%urry "lots, electronegativity is used in
1@
Hauling5s scale, +hile in Cheli0o+s0y "lots the Miede#a scale is used. =oth scales
actually have a good correlation as sho+n ,y Miede#a et al. :@4;. 4he other co3
ordinate is different, ato#ic siCe is used in !ar0en3%urry "lots and electron cell3
,oundary density is used in Cheli0o+s0y5s #ethod. (lthough higher accuracy has
,een esta,lished, so#e e8ce"tions re#ain. 4hese e8ce"tions suggest that
Cheli0o+s0y5s #ethod is still susce"ti,le to so#e i#"rove#ent :1;.
*.$.* &lonsos Method
1n the 12D$s, fro# analysis of ,oth !ar0en3%urry and Cheli0o+s0y #ethods, (lonso
and Si#oCar :1; "ro"osed a sche#e containing all three coordinates >ato#ic siCe,
electronegativity, electron cell3,oundary densityA. 4he suggestion +as also "ro"osed
,y Miede#a and !e Chatel :2B;. =y incor"orating a siCe factor in a ne+ gra"hical
#ethod, they i#"roved on the original Miede#a coordinate sche#e "ro"osed ,y
Cheli0o+s0y. 1n their analysis, each che#ical ele#ent is characteriCed ,y three
"ara#eters- the ato#ic volu#e V , the electronegativity
\

, and the electron

density at the ,oundary of ,ul0 ato#ic cells
b
n
. (s the result,
\

and
s
n
>the
difference of electronegativity and electron density at the ,oundary of ,ul0 ato#ic
cellsA co#,ined into a ne+ "ara#eter,
!
"
, the heat of for#ation of an e/ui3ato#ic
co#"ound, calculated using a se#i3e#"irical for#ula "ro"osed ,y Miede#a,
( ) ( ) # n $ % "
s !
+

B F 1

\
, >E/uation BA
+here H and Q are universal constants and R is another constant +hich deviates fro#
Cero only +hen one of the #etals is "olyvalent +ith p electrons :@?, @D, 24;. 4hen, the
t+o "ara#eters
!
"
and V >e8"ressed as &igner3SeitC radius, R
&
A are used to
construct a t+o3di#ensional #a". 1n this #a", the che#ical ele#ents insolu,le in a
given host are neatly se"arated fro# the solu,le ones ,y a straight line. 4he e8a#"les
1G
and the co#"arisons +ith Cheli0o+s0y5s "lot are sho+n in <igures B>aA and B>,A. 1n
these "a"er, the relative i#"ortance of the three coordinates >ato#ic siCe,
electronegativity and electron cell3,oundary densityA is de#onstratedM also they
e8"lained the success of the sche#es of !ar0en and %urry and of Cheli0o+s0y ,y the
fact that ato#ic siCe and electron cell3,oundary density are strongly correlated in
given class of #etals. Later, (lonso et al. a""lied this #ethod to the "rediction of
solid solu,ility in no,le #etal, transition #etal and sp #etal ,ased alloys :1B, 2?;.
)ones has a""lied this #ethod to the solid solu,ility of t+o light #etals, #agnesiu#
and alu#iniu# :2@;.
(fter the heat of for#ation calculations ,y Miede#a, others succeeded in "redicting
the heats of for#ation of different ,inary alloys fro# ,oth first3"rinci"les and se#i3
e#"irical #ethods :2G31$D;. !uring the last t+enty years and ,ased on calculated
heats of for#ation of alloys and se#i3e#"irical theories +ith "ara#eters such as
electronegativity difference, ato#ic dia#eter and nu#,er of covalent ,onds, a large
nu#,er of "redicted #a8i#u# solid solu,ilities of alloys, design of alloy syste#s or
for#ation of co#"ounds have a""eared :1$2312;. 4his indicates these #ethods still
have vitality in the "rediction of alloy for#ation even though near thirty years has
"assed.
>insert figure B hereA
*.$.1 Zhang 23 Method
Ehang and co3+or0ers used gra"hical #ethods +ith various "ara#etersFcoordinates to
"redict the for#ation of a#or"hous alloys and solid solutions. Several factors affect
the for#ation of a#or"hous alloys and solid solutions, so#e acting against each other
>e/uation GA. :1?, 1B$;.
1D
1n 12DB :1B1;, they a""lied Miede#a5s coordinates to the "rediction of ,inary
a#or"hous alloy for#ation and found that this #ethod +or0ed /uite +ell. More
s"ecifically, they found >1A the ranges of for#a,le and non3for#a,le ,inary
a#or"hous alloys can ,e, to a good e8tent, se"arated ,y a straight line, +hich is
$ 1
1
B2 1$
B F 1
\

,
_

s
n

, >E/uation 4A
+here
\

and
s
n
are the differences of electronegativity and electron density
res"ectivly at the ,oundary of ,ul0 ato#ic cells as #entioned ,eforeM >A of the D
a#or"hous alloys for#ed ,y #elt3/uenching, the "rediction accuracy +as 2.GOM >BA
of the ?4 non3for#a,le a#or"hous alloys, the "rediction accuracy +as @@.GOM >4A of
the 1 a#or"hous alloys for#ed ,y non3#elt /uenching, the "rediction accuracy +as
4G.@O. Lf the total 1?G alloys studied, the overall accuracy +as GG.GO. 4hese results
co#"ared +ell +ith the +or0 done ,y Shi et al. :1B; using ,ond3"ara#etric
diagra#s, in +hich the ,ond "ara#eters
&
r ' F
and
!(V
r ' F
>+here the ' is ato#ic
valence,
&
r
is ato#ic 0ernel radius e/uals a""ro8i#ately the "ositive ionic radius
not including the valence electrons, and
!(V
r
is covalent radiusA +ere used to "redict
the for#ation of ,inary a#or"hous alloys, and the "rediction accuracy +as D$O.
4a0ing the "ara#eters used in Miede#a5s coordinates +ithout the siCe factor, Ehang
:1BB; co#,ined the t+o che#ical coordinates
\

and
B F 1
s
n
into one-
( ) 1 F 1 B2 1$
B F 1 \

s
n y
, >E/uation ?A
and using the radius difference of ele#ents
12
O
1
1
#
# #
x

>E/uation @A
as the other coordinate to constructed a t+o3di#ensional #a". <ro# this, the
definition of conditions for for#ation of ,inary a#or"hous alloys +as i#"roved. 4he
se"aration of the for#a,le and non3for#a,le regions +as given ,y
G? . 1
$? . $

x y
.
4he "rediction accuracy is high- aA of the D a#or"hous alloys for#ed ,y #elt
/uenching, the "rediction accuracy +as DG.DOM ,A of the ?4 non3for#ed a#or"hous
alloys, the "rediction accuracy +as DB.BOM cA of 1 a#or"hous alloys for#ed ,y non3
#elt /uenching, the "rediction accuracy +as @@.GO. Lf the total 1?G alloys studied in
that +or0, the overall accuracy +as DB.4O. 4hese co#"arisons are also sho+n in
4a,le 1. 1t can ,e seen that the "rediction accuracy for the for#ation of a#or"hous
alloys is i#"roved +hen the siCe factor is added to the original Miede#a coordinates
criterion.
>insert ta,le 1 hereA
Ehang and co3+or0ers "ro"osed another gra"hical #ethod, +hich co#,ined
&
r ' F

and
!(V
r ' F
as an electron factor, then together +ith a siCe factor to "rovide t+o
coordinates for the study of solid solu,ility, they descri,ed the for#ation of
a#or"hous alloys :1B4;. 4he t+o coordinates are e8"ressed ,y >1A ,ond3"ara#etric
function
% %
&
x
r
'
x
r
'
1
]
1

,
_

+
B

B
1
cov
and >A half of the e#"irical interato#ic distance
# res"ectively. &here
&
r ' F
is the ratio of ato#ic valence and ato#ic 0ernel radius,
and
!(V
r ' F
the ratio of ato#ic valence and covalent radius. 4he *ernal radius
$
e/uals a""ro8i#ately the "ositive ionic radius.
%
x
is the Hauling electronegativity.
&hen the coordinate "oint of a host ele#ent is re"resented in the chart, the closer is
the "oint of a solute ele#ent to it, the s#aller the differences of the electron factors
and of the siCe factors ,et+een the solute ele#ent and the host ele#ent. Ehang :1B$;
a""lied this #ethod to 1$D$ ,inary and got a "rediction accuracy of 2BO.
Ehang used a #odified electron factor
( )
%B %A
A
!(V
%A
B
&
) )
r
'
)
r
'
y
1
1
]
1

,
_

,
_

B
1
>E/uation GA
as ordinate and
O
1
1
#
# #
x

as a,scissa to search for solid solu,ilities at roo#

te#"erature in 4@$ ,inary alloys. 1n this +or0 the transition #etals of the fourth,
fifth and si8th long "eriods and 1D non3transition #etals are studied. <or each host
ele#ent, a "ara,olic curve

bx a y
can ,e dra+n to se"arate the solu,le ele#ents
fro# the insolu,le ones +ith a criterion of $.? at.O solu,ility at roo# te#"erature.
4he overall relia,ility of this e/uation a""roached 2$O for 4@$ alloys. (lso, it has
,een found that the values of a for each host #etal are "ro"ortional to its cohesive
energies E, and b values are "ro"ortional to
B
$
# E
, +here * is the shear #odulus of
solvent ele#ent, and #
+
is the ato#ic radius of the solvent :1B?;.
1n 122@, Ehang and Liao :1B@; a""lied this #ethod to study the solid solu,ilities for
the ,inary alloy syste#s ,ased on 1B rare earth #etals, and found the solu,le ele#ents
can ,e se"arated fro# the insolu,le ones ,y a "ara,ola

1 1
bx a y , +here x
1
is
defined in e/uation @ and, y
1
is defined in e/uation G. Lr an elli"tical curve
( ) ( ) 1 F F

+ d n y c , x , >E/uation DA
1
+here
# x

and

% %
&
x
r
'
x
r
'
y
1
]
1

,
_

+
B

B
1
cov

. >E/uation 2A
<or the solid solu,ilities in D2G ,inary alloys, the "rediction accuracy +as D2.O for
the "ara,olic se"aration, and 2.DO for the elli"tical se"aration. (lso, in the elli"tical
e/uation, constants , and n +ere de"endent on the coordinates

x
and

y
,
c
+as
"ro"ortional to ( )
F 1
B

# and d +as "ro"ortional E.
1n 1222, Ehang and Liao :14, 1?; su##ariCed different #ethods used ,y the#selves
and others and #ade a co#"arison in ter#s of "rediction accuracy. 4hose results are
sho+n in 4a,le .
>insert ta,le hereA
4he ECS

#ethod, as +ell as 'u#e3Rothery5s rule and the !ar0en3%urry #ethod, are

for "redicting solid solu,ility +ithout considering %i,,s energy. 4hese #ethods are
easy to use ] needing only the "hysical "ara#eters >radii, electronegativity, structureA
of t+o ele#ents :@B;. 4he e8tent of "ri#ary solid solu,ility can ,e derived ,y using
first "rinci"le calculations. <ollo+ing +or0 done ,y others :1BG314B;, Shin et al.
:144; descri,ed the Cu3Si syste# ther#odyna#ically as an e8a#"le of higher order
syste#s >i.e. solute ele#ents in co#"oundsA +ith first3"rinci"les calculations of the R3
Cu
1?
Si
4
"hase and solid solution "hases. =y considering the enthal"y of #i8ing and
%i,,s energies of individual "hases in the Cu3Si ,inary syste#, it +as found that the
e8istence of inter#etallic co#"ounds +ould strongly affect solu,ility li#its.

Hredictions of solid solu,ility of other alloy syste#s using first "rinci"les can ,e
found else+here :14?31@@;.
1.' %olubility prediction using artificial neural net0or.s
(lthough a large nu#,er of researches on solu,ility "rediction have ,een "u,lished in
the last century, fe+ of the# have atte#"ted to "redict the solu,ility /uantitatively.
4he siCe factor has ,een regarded as the #ost i#"ortant factor ,ut has never ,een
/uantitatively "roved. Recently, the authors :1@G; have used one tool of artificial
intelligence, artificial neural net+or0s >(NNsA, to si#ulate the "rocess that 'u#e3
Rothery used to derive the 'u#e3Rothery5s Rules fro# e8"eri#ents. <urther#ore,
these authors atte#"ted to "redict the solu,ility /uantitatively rather than "roduce a
classification of solu,leFinsolu,le ,y this #ethod.
1. %election of input parameters for &44 e5amination of solubility
4he versatility of the (NN "er#its various co#,inations of nu#,er and for#at for
in"ut "ara#eters to ,e ado"ted easily. (ll the "ara#eters that 'u#e3Rothery used
+ere tested even though so#e of the# +ere neglected later ,y 'u#e3Rothery
hi#self. 4he in"ut "ara#eters for the net+or0 include >1A ato#ic siCe "ara#eter, >A
valence "ara#eter, >BA electroche#ical "ara#eter, i.e. electronegativity and >4A
structure "ara#eter of solvent and solute ato#s. 4hree different e8"ressions of these
"ara#eters +ere used to e8a#ine +hich gave the ,est "erfor#ance-
1. 4he ra+ data that 'u#e3Rothery used.
. 4he original collected values for each "ara#eter of solvent and solute ato#s.
B. 4he functionaliCed "ara#eters-
B
iA -or the si.e factor. 4he difference ,et+een the ato#ic dia#eters of solvent
and solute ato#s divided ,y the dia#eter of the solvent ato#s.
iiA -or the valence factor. Lriginal values are used, leaving the neural
net+or0 to decide the relations ,et+een valence of solvents and solutes.
iiiA -or the electroche,ical factor. 4he difference ,et+een that of the solvent
and solute ato#s.
ivA -or the structure para,eter. 4he structures are e8"ressed in three sets of
nu#,ers re"resenting "ri#itive cell di#ensions, angles and syste#s. 4he
three sets are >1A unit cell length, >A a8es angles and >BA >si#"leM ,ase3
centredM face3centredM ,ody3centredA.
&hen the original values of in"ut "ara#eters are used, the training "erfor#ance of the
(NN is /uite good >+ith regression coefficient RS$.22@A ,ut the "rediction of the
testing set is "oor. &hen the functionaliCed values +ere used as in"ut "ara#eters,
,oth the training and testing set of the (NN gave good "erfor#ance. 4hrough a
search of all co#,inations of those "ara#eter for#ats, the ,est for#at of in"ut
"ara#eters +as deter#ined as the functionaliCed values.
(nother uncertainty in the '3R rule is the ato#ic siCe difference- so#e researchers
,elieve the threshold is 14O and others ,elieve it5s 1?O. 4he "erfor#ance of (NN
using the 1?O criterion is slightly higher than that for 14O +hich i#"lies 1?O is a
,etter threshold in the siCe factor.
Using the sa#e a""roach and including the 1?O criterion, the structure "ara#eter +as
introduced in ter#s of +hether the structure of solvents and solutes are the sa#e or
4
not >i.e. 1 sa#e, $ not sa#eA. 4here +as no i#"rove#ent in correlation. 4his indicates
that the structure "ara#eter do not "lay a very i#"ortant role in solu,ility.
1.$ +etermination of the output parameters
<ro# 'u#e3Rothery5s rules, only the "ossi,ility of +hether a co#"onent is solu,le or
insolu,le can ,e "redicted. 'o+ever, it +ould ,e #ore advantageous to atte#"t to
"redict the original value of solu,ility. 4he out"ut "ara#eters are e8"ressed in t+o
+ays-
1A <ollo+ a s"ecialiCed criterion- if the solu,ility of solute #etal in solvent #etal
e8ceeds ? at. O, then it is said that this solute #etal is solu,le in the solvent #etal.
A Lriginal #a8i#u# solu,ility li#its of each alloy syste# are used.
4he results of the "rediction sho+ the (NN can "redict the solu,ility /uantitatively
+ith a s#all #ean #odulus error of 1.@? at.O. Such "rediction is sho+n in <igure 4.
83a8is are e8"eri#ental solu,ility >at.OA fro# e8"eri#ent results and y3a8is are
"redicted solu,ility >at.OA "redicted fro# (NN. Most of the data "oints are located
close to yS8 indicating an accurate "rediction.
1.* +etermination of the relative importance of each rule
1t has ,een recogniCed that each rule has a different influence on solu,ility- the #ost
i#"ortant rule is the ato#ic siCe factor, follo+ed ne8t ,y the electroche#ical factor
>electronegativityA. 'o+ever, these "ara#eters are not +holly inde"endent of each
otherM their inter"lay #a0es the deter#ination of solu,ility very difficult. So the
deter#ination of the relative i#"ortance of each rule is not easy. 1n this research, the
"erfor#ance of the (NN +as evaluated +hen so#e of the rules +ere deli,erately
o#itted. Using the #ean error of the testing set as the #ain criterion for accuracy of
?
the "rediction, ato#ic siCe has the strongest effect ,ecause, +hen it is o#itted, the
error is highest. Electronegativity has a stronger influence than valence. &hen "airs of
"ara#eters are o#itted, the "erfor#ance of the "rediction ,eca#e +orse. L#ission of
the structure "ara#eter only had s#all effect on the "erfor#ance of the (NN, +hich
i#"lies that the structure "ara#eter does not "lay a very i#"ortant role, and indeed
'u#e3Rothery did not include it in 12B4.
6.' %ummary
!uring the decades after 'u#e3Rothery5s Rules +ere "u,lished, the value and
relia,ility of the# has ,een discussed e8tensively. 4hey have ,een de,ated, e8tended
and refined in different +ays, as #entioned in the te8t. (lso, as 'u#e3Rothery and
co3+or0ers stated at the ti#e +hen they first raised these rules- K1n general, the
solu,ility li#it is #ainly deter#ined ,y these factors, and it is their inter"lay that
#a0es the results so co#"le85 :@;. 'o+ever, even though one cannot "redict the solid
solu,ility li#its accurately using 'u#e3Rothery5s rules, they are still useful
guidelines for 9udging the solu,ility of alloy syste#s or for#ation of inter#etallic
co#"ounds.
Massals0i :4; suggests that although 'u#e3Rothery5s rules are i#"ortant, insufficient
docu#ented e8a#"les of "ractical a""lication and "redictive ca"a,ility have ,een
de#onstrated so far and this is a real challenge to the future of alloy develo"#ent and
of inter#etallic co#"ound for#ation. (t "resent, it is necessary to accu#ulate a large
a#ount of +or0 to investigate +hich rules have ,een deter#ined and +hich have not.
Ne+ investigation tools, such as (1 >(rtificial 1ntelligenceA, can ,e used to validate
those rules and to e8"lore ne+ "ara#eters or rules in the future.
@
&c.no0ledgments
4he authors are grateful to School of Engineering and Materials Science of Queen
Mary, University of London to su""ort this +or0 ,y "roviding research studentshi" to
W.M. Ehang.
G
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B2
4a,le Ca"tions-
4a,le 1 Co#"arison of the for#ation of ,inary a#or"hous alloys using
different coordinates >redra+n fro# :12;A
4a,le Co#"arison of the "rediction of solid solu,ilities ,y different #ethods
>redra+n fro# :1?;A
4$
4a,les-
4a,le 1
Hure Miede#a5s
coordinate criterion
Miede#a5s
coordinate "lus siCe
factor
=ond3"ara#etric
diagra#
>1A (#or"hous alloys
,y #elt /uenching
total D D B
+rong @ 1$ B
accuracy >OA 2.G DG.D 2$.@
>A Non3for#a,le
a#or"hous alloys
total ?4 ?4 ?G
+rong 1D 2 G
accuracy >OA @@.G DB.B DG.G
>BA (#or"hous alloys
,y non3#elt
/uenching
total 1 1 BD
+rong 11 G 1$
accuracy >OA 4G.@ @@.G GB.G
4otal accuracy >OA >1A Q >A D.4 D@ DD.D
>1A Q >A Q >BA GG.G DB.4 D4.B
41
4a,le
No. of alloy syste#s and the "rediction accuracy
4otal No. Hrediction accuracy O
'u#e3Rothery5s rule >siCe factor onlyA 14B @G.@
!3% Method 14?? G@.@
Cheli0o+s0y Method 12 D
(lonso Method B4 2$
Ehang =& Method >"ara,ola se"arationA BD@4 DG.
Ehang =& Method >elli"se se"arationA BD@4 2$.B
4
)igures captions:
<igure 1 4he electronegativity vs. the #etallic radius for a coordination nu#,er
of 1 >!ar0en3%urryA #a" for 4a as the solvent. >4a0en fro# :?2;A
<igure . >aA !ar0en3%urry #a" for Mg as host #etal. >,A Cheli0o+s0y #ethod
for Mg as host #etal >ta0en fro# :11;A
<igure B >aA Cheli0o+s0y5s "lot for the analysis of solid solu,ility in <eM >,A
(lonso "lot for analysis of solid solu,ility in <e, the t+o continuous lines se"arate the
insolu,le ele#ents fro# the rest. >ta0en fro# :1;A
<igure 4. Hrediction of solu,ility using B functionaliCed "ara#eters- ato#ic siCe,
valency and electronegativity. >aA 4raining set, >,A 4esting set, >cA &hole set.
4B
<igures-
<igure 1
44
>aA
>,A
<igure
4?
>aA
>,A
<igure B.
4@
0 20 40 60 80 100
-20
0
20
40
60
80
100
Experimental Solubility T (at.%)
P
r
e
d
i
c
t
e
d

S
o
l
u
b
i
l
i
t
y

A

(
a
t
.
%
)
Best Linear Fit: A = (0.977) T + (0.23)
R = 0.993
0 20 40 60 80 100
-20
0
20
40
60
80
100
Experimental Solubility T (at.%)
P
r
e
d
i
c
t
e
d

S
o
l
u
b
i
l
i
t
y

A

(
a
t
.
%
)
Best Linear Fit: A = (0.962) T + (-1.19)
R = 0.992
0 20 40 60 80 100
-20
0
20
40
60
80
100
Experimental Solubility T (at.%)
P
r
e
d
i
c
t
e
d

S
o
l
u
b
i
l
i
t
y

A

(
a
t
.
%
)
Best Linear Fit: A = (0.966) T + (0.0162)
R = 0.992


Data Points
Best Linear Fit
A = T
(a) Training set (b) Testing set
(c) Whole set
<igure 4
4G