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Scaling Theory of Circular Surface Micelles of Diblock Copolymers

Artem M. Rumyantsev*
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sı Supporting Information

ABSTRACT: Surface micelles of AB diblock copolymer have a

three-dimensional (3D) core formed by B blocks and a two-
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dimensional (2D) corona consisting of A blocks strongly adsorbed

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and swollen at the air−liquid interface. A scaling theory of circular

spherical micelles is developed by describing flat corona within the
2D Daoud−Cotton model. The power-law dependencies of their
sizes and the aggregation number p on the block lengths NA and NB
are predicted for the limits of starlike and crew-cut morphologies.
Owing to the corona’s spatial confinement, the derived laws differ
from those for usual micelles with 3D corona forming in the
solution bulk. If solvent quality is Θ for 2D corona chains, theory
−0.67
predicts pst ∼ N0A N0.5
B and pcc ∼ NA N0.83
B for starlike and crew-
cut micelles, respectively. In the recent systematic experiments [J.
Phys. Chem. Lett. 2022, 13, 5380], numerical fitting of the results (corresponding to a wide crossover region between crew-cut and
starlike limits) with a single power law led to p ∼ N−0.48 A N0.7
B ; these empirical exponents fall within the range theoretically found
herein. Our predictions for the core radius and corona thickness are in similar agreement with the experiment, both for Θ and a good
solvent quality for the corona. Theory extension to micelles with quasi-planar 2D cores demonstrates that the core morphology
weakly affects scaling laws. The developed approach provides insight into mechanisms controlling the interfacial self-assembly of
diblock copolymers.

I. INTRODUCTION Vilanove and Rondelez systematically studied the properties

Conformational statistics of polymers and spatial correlations of PMMA 2D solutions and found that their surface pressure Π
increases with the 2D concentration of monomers c2D as
between their monomers are sensitive to confinement. If
confinement is strong, it may effectively reduce the dimension- y
c 2D (1)
ality of the space, d, in which polymers are located. Polymer
chains, which are strongly adsorbed at the planar solid or liquid with y ≈ 10.5 Scaling theory of 2D semidilute solutions predicts8
interface, can adopt only flat conformations and can be therefore
considered two-dimensional (2D) polymers. Reducing d from 3 d 2
y= =
to 2 changes the most universal and fundamental features of d 1 d=2 2 1 (2)
polymer statistics, such as the scaling exponents controlling
system equilibrium properties and dynamics.1−3 so the result obtained suggests that the 2D Flory exponent for
An example of a strictly 2D polymer system is a monolayer4 of PMMA chains is ν ≈ 0.56.5 Considering the exponent for 2D
poly(methyl methacrylate) [PMMA] chains spread at the air− polymers in Θ (tricritical) point equals ν = 4/7 ≈ 0.57,9 the air−
water interface. PMMA is completely insoluble in water, i.e., water interface is a 2D Θ solvent for PMMA.10
water should be considered as a nonsolvent for the polymer in a One can argue that generally speaking, for a given polymer,
usual three-dimensional (3D) sense. However, PMMA is the 3D solvent quality of water and 2D solvent quality of the air−
water interface are independent. The former is defined by
soluble at the air−water interface and can form a 2D solution.5−7
polymer−water interactions, while the latter is controlled by the
The latter is normally prepared as follows. PMMA is first
interplay between polymer−water, polymer−air, and water−air
dissolved in an organic solvent such as chloromethylene or
chloroform, and then this solvent is spread on a water surface.
The high volatility of organic solvents provides their fast Received: May 2, 2023
evaporation, while polymer chains remain pinned onto the air− Revised: June 28, 2023
water interface. When the initial polymer concentration is Published: July 20, 2023
sufficiently high and the water interface area is limited, PMMA
chains contact/cross each other, thereby forming a 2D
semidilute solution.
© 2023 The Author. Published by
American Chemical Society https://doi.org/10.1021/acs.macromol.3c00851
6162 Macromolecules 2023, 56, 6162−6172
Macromolecules pubs.acs.org/Macromolecules
interactions with due regard to polymer and water molecules’
orientation at the interface. To illustrate that, PMMA and
poly(2-vinylpyridine) [P2VP] can be compared to each other.
Both polymers are insoluble in water at neutral pH when P2VP is
not ionized. At the same time, the 2D solvent quality of the air−
water interface for P2VP is good,11 with the 2D exponent equal
to ν = 3/4,12 which suggests the theoretical value of y = 3 in the
pressure−concentration relationship given by eq 1. The latter is
in agreement with the experimental result of 2.75 reported for
P2VP monolayers.11 The slopes ranging between 2.7 and 2.85
were also reported for semidilute monolayers of other polymers
that swell in 2D.5,13
Independent and often different 3D and 2D solvent qualities
for the same polymer, such as simultaneous attractions between
P2VP monomers in water14,15 (as well as air) but their
repulsions at the water−air interface,11 albeit experimentally
established, may seem counter-intuitive and deserve clarifica-
tion. Monomers of most surface active polymers are
amphiphilic. This drives their anchoring to the interface
accompanied by fixing the preferential orientation with respect
to it.16−18 The resulting relative orientation (distribution
function) of the adsorbed monomers becomes substantially
anisotropic, in contrast to isotropic in water bulk. Combined
with the orientation-dependent monomer−monomer interac-
tions (remember dipoles or Onsager rods), this leads to 3D and
2D solvent qualities not necessarily coinciding with each other.
One more reason is that the structure of the water, e.g.,
orientation and clustering of the molecules, in the surface layer
and bulk are also substantially different.19
While the properties of 2D polymers are well understood,1−3
the physics of polymer systems, which are only partially
confined, is less explored. An experimentally relevant example
is micelles of AB diblock copolymer with 3D core and 2D
corona. In usual micelles forming in the solution bulk, insoluble
core blocks B collapse and provide the tendency to aggregation;
the latter is hindered by the repulsions between the soluble
blocks A forming the corona, which ensures micelle solubility
and stability. If diblock copolymer aggregation happens at the
interface, which strongly and selectively adsorbs corona blocks
A, the corona becomes effectively 2D. In the experiment, air−
water surface micelles of polystyrene-b-poly(2-vinylpyridine)
[PS-b-P2VP] or polystyrene-b-poly(methyl methacrylate) [PS-
b-PMMA] are produced in the same way as polymer monolayers
(Langmuir monolayers).11,20−23 Because both blocks are
strongly hydrophobic, diblock copolymers are first dissolved in
chloroform where they are completely soluble and any
micellization is absent. After depositing the droplet of this
solution at the air−water interface and chloroform evaporation,
PS blocks start to aggregate. Their attractions are balanced by
2D short-range repulsions between the P2VP or PMMA blocks,
which are adsorbed at the air−water interface. As in
homopolymer monolayers of P2VP and PMMA, corona blocks
adopt flat interfacial conformations and their strong adsorption
is promoted by insolubility in water bulk.
The resulting micelles with 3D core and 2D corona have been
studied by different groups.11,20−28 The empirical scaling laws
controlling the aggregation numbers and dimensions of the core
and corona have been obtained,11 which noticeably differ from
those for usual micelles with 3D core and 3D corona.29 The
objective of this work is to develop a scaling theory of surface
diblock copolymer micelles, which would take into consid-
eration the effect of 2D confined corona and predict how the
6163
Article
scaling laws for the surface micelles’ properties should change as
compared to their solution counterparts.
II. SCALING THEORY OF MICELLES WITH 3D CORE
AND 2D CORONA
We consider AB diblock copolymers with flexible blocks
containing NA and NB statistical segments of equal size, aA =
aB = a. Diblock copolymers form micelles with the aggregation
number p. The micelle corona consists of A chains adsorbed at
the flat air−liquid interface. We assume that adsorption is strong,
with the adsorption energy per monomer −δkBT at least equal to
the thermal energy, δ ≥ 1. This provides the normal height of the
corona of the order of a irrespective of the 3D solvent quality of
liquid for corona chains. The strong adsorption limit is
reasonable for water-insoluble surface active polymers such as
PMMA and P2VP. More importantly, it will be demonstrated in
Section IV.2 that this assumption does not limit the generality of
derived scaling laws: They remain valid for weakly adsorbed
corona chains, δ ≪ 1, under 3D good solvent conditions for
them. Thus, the corona is viewed as a planar 2D semidilute
solution, and its lateral thickness is denoted H (Figure 1a). In
Figure 1. (a) Top view of the surface micelle with the core radius R and
the corona thickness H. Corona is presented as the 2D melt of blobs
with the size ξ(r), which increases from the core interface to the
periphery. (b) Side view of the micelle core at the liquid−vapor
interface. Core shape and the contact angles θ1 and θ2 can be defined
from the Neumann construction for the surface tensions, γ⃗1 + γ⃗2 + γ⃗0 +
γ⃗ex = 0.
contrast, the micellar core has a nonplanar 3D shape, as shown in
Figure 1b. The core is in direct contact with liquid, i.e., there are
no A blocks adsorbed at the core−liquid interface. The external
surface pressure is zero.
To find the equilibrium structure of the micelle, we construct
and minimize the free energy per one AB copolymer chain. It
includes three terms taking into account (i) the extension of and
repulsions between A blocks in the corona, (ii) the excess free
energy at the core−air and core−liquid interfaces, and (iii) the
stretching of B block in the core
Ftot = Fcorona + Fsurf + Fcore (3)
In what follows, we express all energies in units of kBT and all
lengths in a units.
When the adsorption of corona blocks is strong, the junction
points between A and B blocks are at the edge of the core,
namely, at the three-phase circular contact line between the core,
the liquid, and the vapor. Following the Daoud−Cotton
model30−32 applied to the 2D case, the corona of the micelle
can be considered the melt of 2D blobs, as seen in Figure 1a. The
geometry of the problem suggests that the blob size linearly
increases with the distance r from the micelle center
https://doi.org/10.1021/acs.macromol.3c00851
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r The extra contribution is induced by repulsions between the

(r )
p (4) corona chains, which diminish with increasing the core radius.
Following the surface tension definition, it can be calculated as
Chain statistics within each blob are controlled by 2D solvent
quality for the planar corona chains, and the number of l
o p2 /R2 , st
(pFcorona) 1 (pFcorona) o
o
monomers in the 2D blob is = = m
o
ex
S0 2 R R o
o Hp2 /R3 , cc
ij r yz
1/ n
g (r ) 1/
(r ) jj zz (11)
jj p zz
k { (5) 2
Here, S0 = πR is the area of the liquid−vapor interface
For athermal solvent, the exponent ν for d = 2 dimensions “screened” by the core. We emphasize that the described surface
coincides with the Flory exponent, ν+2D = 3/(d + 2) = 3/4.12 For tension renormalization should be applied only to the Neumann
Θ solvent (tricritical point), the exact value νΘ2D = 4/7 ≈ 0.57 was construction but not to the surface free energy. The Neumann
÷
obtained by Duplantier and Saleur9 and agrees well with those triangle now implies 1 + 2 + 0 = 0, and the contact angle
from renormalization group calculations33 and experimental values are defined by
surface pressure isotherms.5,7,11,34 Recall that in 2D, ν = 1/2 2 2 2 2 2 2
corresponds to poor solvent conditions when the collapse of 0
+ 1 2 0
+ 2 1
corona chains leads to micelle aggregation; this case is briefly cos 1 = ; cos 2 =
2 01 202 (12)
discussed in Section IV.1.
The thickness of the corona, H, can be found from the In what follows, it will be demonstrated that γex ≃ γ0. Therefore,
normalization condition written for A monomers the nonspreading condition for the micelle core is given by γ1 +
R+H γ2 ≳ γ̃0 ≃ γ0 and, at the scaling level of accuracy, coincides with
g (r )
2
r dr p(2 1)/
[(R + H )1/ R1/ ] pNA that in the absence of corona.38 We assume it is fulfilled so that
R (r ) the micelle core never wets the liquid−air interface. In other
(6) words, θ1 and θ2 do not tend to zero (it would be the case if, e.g.,
The analytical closures between the corona thickness and the γex diverge) and the core remains 3D. The opposite scenario of
aggregation number can be obtained in the limits of starlike the core spreading at the air−liquid surface is considered in
(“st”) and crew-cut (“cc”) micelles, R ≪ H and R ≫ H, Section V.
respectively The volume of the spherical caps is given by

Hst p1 NA (7) R3 2 3 cos i + cos3 i

Vi = × 3
3 sin i (13)
(1 )/
i py
Hcc NA jjj zzz with i = 1 and 2 for the top and bottom ones, respectively.
kR{ (8)
Assuming that the core is solvent-free, the space-filling condition
The free energy of the corona block is equal to the number of V1 + V2 = pNB can be used to find the core radius
blobs in it
R = ( pNB)1/3 (14)
R+H dr i Hy
Fcorona p lnjjj1 + zzz Here, the numerical prefactor
R (r ) k R{
ÄÅ
l
o p, st ÅÅ 2 3 cos + cos2
o
o
1 ÅÅ 1 1
o ( 1 , 2) = Å
o
m 1/ 3 ÅÅÅÇ sin3 1
o
o ij p yz
o j z
o A j R z , cc
o
N ÑÉÑ
n k { (9) 2 3 cos 2 + cos2 2Ñ
ÑÑ
+ ÑÑ
sin 3 2 ÑÑÖ (15)
Under athermal solvent conditions, our results for starlike
regime, eqs 7 and 9, coincide with those reported by Halperin is on the order of unity and expresses the dependence of the
and Joanny for 2D polymer stars with p arms.35 radius on the contact angles (i.e., on the three surface tensions)
To find the two other contributions to the total free energy, but is independent of the core size and other problem
Fsurf and Fcore, the shape of the core should be first defined. It is parameters. The exponent 1/3 in eq 14 demonstrates that the
controlled by the interplay of the surface tensions between the core has essentially 3D rather than a quasi-planar 2D shape. The
core, liquid, and vapor (air), as demonstrated in Figure 1b. The core normal height, which is the sum of the cap heights,
effect of gravity can be neglected because the characteristic increases linearly with R. For micelles with a quasi-2D, disk-like
capillary length of the problem is in the millimeter range36 and core of a fixed height, the resulting scaling exponents are derived
exceeds by ∼5 magnitudes the core size, which is from tens to in Section V and differ from what is found below.
hundreds of nanometers. In this case, the core has a lens shape The interfacial area of the core−vapor interface is equal to that
and consists of two spherical caps with equal base radii, R. In the of the spherical cap, S1 = 2πr21(1 − cos θ1), where r1 = R/sin θ1 is
absence of the micelle corona, one could have applied the its curvature radius. The area of the core−liquid interface S2 can
Neumann construction,37 γ⃗1 + γ⃗2 + γ⃗0 = 0, to find the respective be found similarly. The excess surface energy of the core
contact angles θ1 and θ2. However, the presence of the corona therefore equals
grafted to the core generates additional surface tension γex,
which renormalizes the liquid−vapor surface tension γ0 S
1 1
+ 2S2 S
0 0 0
R2
Fsurf = =
0 0 = 0 + ex (10) p p (16)

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Here, we used γ0 rather than γ̃0 because the corona effective single AB diblock copolymer adsorbed at the liquid−vapor
contribution to the surface tension is taken into account by the interface; this is a necessary prerequisite for micellization.
corona term, Fcorona. The introduced function β(θ1, θ2) ≃ 1 is the The excess surface tension is equal to
numerical prefactor, which depends only on the surface tension
values and Neumann’s triangle sides/angles pst2
ÄÅ ÉÑ ex
R st2 0
ÅÅ (1 cos 1) 1 ÑÑÑÑ
(23)
ÅÅ 1 2(1 cos 2)
( 1, 2) = 2 ÅÅ + Ñ
ÅÅ
ÅÇ sin 2 1 sin 2 2 2 ÑÑÑÑ Owing β(θ1; θ2) ≃ 1, γex is on the order of γ0 and the shape of the
0 0 Ö core is only moderately affected (flattened) by the corona chains
(17) grafted to it. If all of the numerical coefficients had been retained
Finally, the conformational contribution due to the core block in the analysis, closure given by eq 23 (together with eqs 12 and
stretching obeys1,2 17) would have specified the exact values of the contact angles,
θ1 and θ2.
R2 Micelles have starlike morphology when their soluble blocks
Fcore
NB (18) A are sufficiently long, NA ≫ Nst/ccA . The position of starlike to
crew-cut crossover
Here, the free energy of the core block compression in the
perpendicular direction, Fcore,⊥ ≃ NBα2/R2, has been omitted. It NAst/cc ( NB)1/2 ( (3 2)/4
0) (24)
is demonstrated in the Supporting Information that Fcore ≫
Fcore,⊥ because, for micelles with essentially 3D cores, lateral is found from Hst ≃ Rst.
stretching of the core block is much stronger than its In the opposite case, NA ≪ Nst/cc A , micelles have crew-cut
compression in the direction normal to the surface. structure, and their free energy is defined by
We are now in a position to perform the minimization of the
total free energy Ftot(p) with respect to the aggregation number cc p2/3 ( NB)2/3 2/3 p2/3
Ftot(p) NA + 0 +
p. The dimensionless functions α(θ1; θ2) ≃ 1 and β (θ1; θ2) ≃ 1 ( NB)1/3 p1/3 NB1/3
are retained to prove that γex ≃ γ0 and that the core has a 3D (25)
shape. For starlike micelles, according to eqs 9, 16, and 18, the
free energy per diblock copolymer chain takes the following Again, the last contribution due to the core block elasticity is
form negligible if the blocks are long, Acc = β2γ20N3ν/(1−ν)
A α4(2+ν)/3(1−ν)
NB ≫ 1. The interplay between the second (interfacial) term
st 2/3 NB2/3 2/3 p2/3 promoting aggregation and the first (corona) term restraining it
Ftot(p) p+ 0 + results in
p1/3 NB1/3 (19)
3 /(2 + )
The first two terms in eq 19 dominate provided that the diblock ij 0 yz
pcc jj zz ( NB)(2 + 1)/(2 + )
copolymer is sufficiently long, i.e., the parameter Ast = γ1/2
0 NB is
jj N zz
large, Ast ≫ 1. In this case, the balance between the corona and k A{ (26)
surface free energies leads to the equilibrium aggregation /(2 + )
number jij 0 zyz
R cc jjj zzz ( NB)(1 + )/(2 + )

pst ( )3/4
( NB) 1/2 k NA { (27)
0 (20)
2(1 )/(2 + )
Substituting this result into eqs 7 and 14, one can find the Hcc ( 0) NA3 /(2 + )
( NB)(1 )/(2 + )
(28)
dimensions of starlike micelles
Using Rcc ≃ Hcc to find the crossover between crew-cut and
1/4
R st ( 0) ( NB)1/2 (21) starlike regimes reproduces eq 24. The dominant free energy
2/(2+ν) ν/(2+ν)
terms are Fcc cc
corona ≃ Fsurf ≃ (βγ0) NA (αNB)1/(2+ν), and
Hst ( 3(1 )/4
NA( NB)(1 )/2 the core contribution was neglected owing to Fcc cc
core/Fcorona ≃
0) (22) −(1−ν)/(2+ν)
Acc ≪ 1 for Acc ≫ 1. Similar to the case of starlike
It should be noted that the aggregation number and the core micelles, the consistency of our analysis is supported by γex ≃
radius of starlike micelles are independent of the corona block βγ0. The latter serves as the universal condition to define the
properties such as the corona block length, NA, and 2D solvent contact angles for both crew-cut and starlike regimes.
quality for A block, ν. The exponent for the corona thickness’ The key insight from eqs 20−22 and 26−28 is that they
dependence on NA coincides with that for a single A chain, Hst ∼ provide decoupling into simple, power-law dependencies on the
NνA. These results, also known for usual bulk starlike micelles diblock copolymer block lengths, NA and NB, and more
with 3D corona,29,39 should be attributed to relatively weak complicated dependence on the surface tensions; the latter is
repulsions between corona chains. Indeed, eq 9 demonstrates expressed by the combination of γ0, α, and β. For instance, the
that the free energy of short-range repulsions in starlike corona is micelle parameters are non-power-law functions of γ0 because α
a very weak (logarithmic) function of the corona thickness. and β depend on γ0 in a more complex way (see eqs 15 and 17).
Since logarithmic factors are neglected, at the scaling level of However, if all three surface tensions γ0, γ1, and γ2 change
accuracy, conformations of A blocks do not affect pst and Rst. simultaneously by the same number of times x, then the core
A comparison of the dominating free energy terms, Fstcorona ≃ shape and α and β values remain unchanged so that the
Fstsurf ≃ (βγ0)3/4(αNB)1/2, and the neglected contribution, Fstcore ≃ dependence of p, R, and H on the surface tensions (i.e., on the x
−1/2
αβ1/2γ1/2 st st 1/2 1/2
0 , yields Fcore/Fcorona ≃ (β γ0 NB/α) ≃ A−1/2
st ≪1 factor) becomes power-like; the respective exponents are equal
and demonstrates the consistency of our analysis. Physically, this to those for γ0 in eqs 20−22 and 26−28. In what follows, we
inequality ensures collapsed conformations of the core block in a focus on dependencies of the micelle properties on the diblock
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Figure 2. Scaling dependencies of (a, b) the aggregation number p and (c, d) dimensions of surface diblock copolymer micelles on the length of the
corona and core blocks, NA and NB. Core radius R and corona thickness H are shown with solid and dash lines, respectively. Blue and red colors
correspond to Θ and good solvent conditions.
ν
copolymer architecture, NA and NB, as they are the most and H+cc ∼ N9/11
A . In contrast to starlike micelles with Hst ∼ NA,
universal and relevant to the experiment. these exponents are higher than the respective values for a single
The main results of our scaling analysis for starlike and crew- A block, νΘ2D = 4/7 and ν+2D = 3/4. Thus, in crew-cut aggregates,
cut micelles are summarized in Figure 2 and Table 1, where ν+2D repulsions between corona chains are sufficiently strong to
induce their high stretching.
= 3/4 and νΘ2D = 4/7 were used to calculate the exponents. In An interesting feature is that most of the exponents for starlike
crew-cut micelles, the corona thickness increases as HΘcc ∼ N2/3
A and crew-cut surface micelles are remarkably close to each other,
especially for the core and corona dimensions. For instance, in a
Table 1. Scaling Laws for Circular Surface Micelles with 3D good solvent, the corona thickness in starlike and crew-cut
Core and 2D Coronaa regimes obeys H+st ∼ N0.75 0.13 + 0.82 0.09
A NB and Hcc ∼ NA NB . For usual
aggregation corona diblock copolymer micelles with 3D corona, the difference
regime number, p core radius, R thickness, H between starlike29,39 and crew-cut micelles29,40 would be
Θ theory, starlike ∼N0.0
A NB
0.50
∼N0.0
A NB
0.50
∼N0.57
A NB
0.21 noticeably higher: H+st ∼ N0.59 A N0.16
B versus H+cc ∼ N0.81
A N0B if
solvent theory, crew- −0.67 0.83
∼NA NB −0.22 0.61
∼NA NB 0.67 0.17
∼NA NB using ν+3D = 0.588.29 This result can be explained as follows. In
cut crew-cut micelles, the corona can be viewed as the planar
experiment ∼N−0.48
A N0.7
B ∼N−0.09
A N0.49
B ∼N0.72
A NB
0.09
polymer brush of A blocks, and Hcc ∼ NA if the grafting density σ
(ref 11) is fixed. (In equilibrium micelle, σ depends on NA, which leads to
+ theory, starlike ∼N0.0
A NB
0.50
∼N0.0
A NB
0.50
∼N0.75
A NB
0.13
the exponents lower than unity.) Corona stretching in starlike
solvent theory, crew- ∼N−0.82 N0.91 ∼N−0.27 N0.64 ∼N0.82 0.09

cut
A B A B A N B micelles is much weaker, Hst ∼ NνA, and depends on ν. Reducing
experiment ∼N−0.72 N0.7 ∼N−0.13 N0.49 ∼N0.63 0.09 the corona dimensionality from d = 3 to 2 makes conformations
A B A B A NB
(ref 11) of A blocks in starlike micelles more extended
a
Different exponents correspond to starlike or crew-cut morphology 3D = 1/2 2D = 4/7 (29)
of micelles and to theta (Θ) or good (+) solvent quality for the
corona blocks. Theoretical scaling laws are derived herein, and + +
experimental scaling laws are due to ref 11. 3D 3/5 2D = 3/4 (30)

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They become more similar to strongly stretched conformations
typical for crew-cut micelles. Therefore, structural differences
between crew-cut and starlike regimes decrease as d for the
corona goes down. This explains a higher similarity between the
scaling laws for starlike and crew-cut surface micelles with 2D
corona compared to their bulk counterparts. The systematic
comparison between micelles with 2D and 3D corona is
provided in the Supporting Information.
III. COMPARISON TO EXPERIMENT
Close scaling exponents for starlike and crew-cut regimes imply
that the universal scaling should be experimentally observed in a
very wide range of the NA and NB, almost without the change in
the slope at the crossover (see Figure 2c,d). This behavior has
been recently reported in an excellent experimental work by Kim
and Kim,11 who studied diblock copolymer self-assembly at the
air−water interface. They provided empirical scaling laws, which
fit not only their own results but also the data from the
literature.21,23−28 The cases of good and Θ solvent for corona
were explored by considering PS-b-P2VP and PS-b-PMMA
copolymers, respectively. Varying the length of PS (B) and
P2VP (A) blocks led to the following empirical exponents for
good solvent conditions
+
pexp N A 0.72NB0.7
(31)
+ Here, c2D is the 2D concentration of
R exp N A 0.13NB0.49 (32)
+
Hexp N A0.63NB0.09 (33)
A comparison between these results and the theoretical
predictions is summarized in Table 1 and demonstrates their
good agreement. All six empirical exponents are within or very
near the theoretically predicted range. When scaling laws for
crew-cut and starlike micelles are close and the theoretical range
of the exponents is narrow, as for the core and corona
dimensions, their accordance with the experimental data is
remarkable. For instance, the empirical law for R+exp given by eq
32 is very close to our predictions for R+st ∼ N0A N0.5 + interface. Single micelles are not stable, and attractions between
B and Rcc ∼
NA−0.27 0.64
NB . We note that the moderate difference between
theory and experiment should be (at least partially) attributed to
the experimental uncertainty and fitting procedures. For
example, it was reported that changing the latter leads to H+exp
∼N0.58 0.14
scaling for the corona size,11 which slightly differs
A NB
from eq 33. These values are also consistent with the
theoretically anticipated window.
All of the above is also true for the Θ solvent conditions.
Surface micelles of PS-b-PMMA obey empirical laws
pexp N A 0.48NB0.7 (34)
R exp N A 0.09NB0.49
(35)
Hexp N A0.72NB0.09 (36)
which are also close to the theoretical predictions outlined in
Table 1.
It should be noted that the empirical exponents were obtained
by fitting experimental data with the single power law.11 The
experimental points fitted can be found in Table S1 in the
Supporting Information of ref 11 and correspond to the micelles
with 0.2 ≤ H/R ≤ 2, i.e., to the broad crossover between crew-
cut and starlike regimes of circular micelles. This clarifies why
6167
Article
the empirical exponents are not exactly equal to the limiting
theoretical predictions for starlike and crew-cut morphologies
but fall in between them. (Similar correspondence between the
limiting theoretical and empirical exponents has been recently
reported for complex coacervate core micelles forming in
aqueous solutions.41,42) Empirical exponents for R and
especially p demonstrate their substantial dependence on NA.
They are closer to crew-cut rather than the starlike values as, for
starlike micelles, pst and Rst are independent of NA. This should
be potentially attributed to the range of the experimental data
available, which mainly represents H/R values lower than
unity.11
In addition, the competition between the thermodynamic and
kinetic factors22 in the formation of surface micelles with PS core
is to be elucidated.
Our results were derived for zero surface pressure, Π = 0. If
external pressure Π is applied, micelle coronae come into
contact and repel each other. When corona deformation is
substantial (see the Supporting Information for details and
derivation), the relationship between the area per one
monomer and the pressure is given by
l
o
o
1/8
,
1 (2 1)/2 o
m
o
o
c 2D o
n
1/3
, + (37)
monomers at the
interface occupied by overlapping coronae. The experimental
exponent for good solvent, −0.36, obtained for the compressed
layers of PS-b-P2VP micelles11 is in agreement with the theory.
The prediction for Θ solvent condition is to be tested, e.g., for
PS-b-PMMA micelles.
IV. THEORY EXTENSION AND GENERALIZATION
IV.1. Micelles in Poor Solvent for 2D Corona Chain.
Brief remarks should be made for the case of 2D poor solvent for
corona chains, ν−2D = 1/2. Under these conditions, corona blocks
form a dense continuous monolayer at the vapor−liquid
coronae induce their aggregation. The resulting layer is
nanopatterned, likely with long-range (e.g., hexagonal) order.
For starlike micelles, according to eqs 20−22, the period of the
nanostructure follows H−st ∼ N1/2 1/4
A NB , the number of the chains
in the elementary (Wigner-Seitz) cell is p−st ∼ N1/2B , and the core
radius is R−st ∼ N1/2 B . The same scaling was reported by
Kramarenko et al.43,44 for AB diblock copolymer surface
micelles, which form at the solid interface in case of very strong
adsorption of the A block to the substrate.45 In the limit of crew-
cut micelles, one should also consider the possibility of forming
noncircular aggregates (stripes or worms).44
IV.2. Generalization to Weakly Adsorbed Corona. The
results of Section II can be extended to weakly adsorbed corona
chains, with the adsorption energy per monomer low compared
to the thermal energy, δ ≪ 1. Consider the case when 3D liquid
and 2D interface solvent qualities are both good/athermal for
corona blocks, and the respective ν exponents are equal to ν+3D ≈
3/5 and ν+2D = 3/4. Each corona chain now consists of the 3D
spherical adsorption blobs of the size ξads, which is equal to the
corona height in the normal direction. The number of
monomers gads within the adsorption blob is defined by 3D
+
solvent quality, gads ≃ ξ1/νads
3D
d
≃ ξ5/3
ads . According to the blob
definition, the adsorption energy per blob is equal to the thermal
energy, δgϕads ≃ 1, where ϕ is the so-called crossover exponent
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Macromolecules 2023, 56, 6162−6172
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and gϕads is the number of monomers within the blob in contact it reads Hst ≃ δ1/4 p1/4 3/4
st NA and coincides with the size of the
with the interface.49,50 For the sake of comparison with ref 35, adsorbed star polymer with pst arms derived by Halperin and
we follow that work assuming ϕ ≈ 3/5. (Recent studies, Joanny.35
however, indicate that the crossover exponent in the athermal For crew-cut micelles, the generalized eqs 26−28 take the
solvent is rather 0.485 ≈ 1/2,51−54 which would not change the following form:
results much.) This leads to the following corona height and the 3/11 9/11
number of monomers in the adsorption blob49,50 pcc 0
N A 9/11NB10/11 (45)
+
3D / 1
(38) 1/11 3/11
ads R cc 0 N A 3/11NB7/11 (46)
1/ 5/3
gads (39) 3/11 2/11 9/11 1/11
Hcc 0 NA NB (47)
We note that ξads and gads are independent of the radial
coordinate, r. The lower the adsorption strength δ, the weaker the repulsions
The corona of the micelle remains effectively flat, and the 2D in the 2D corona and hence the higher the micelle aggregation
Daoud−Cotton construction shown in Figure 1a remains valid. number. For the same reason, corona lateral thickness is a
The size of the 2D blob is still defined by eq 4 and increases decreasing function of δ.
linearly with the distance from the micelle center, ξ(r) ≃ r/p. It should be emphasized that, for both crew-cut and starlike
Compared to the strong adsorption regime, the only difference is micelles, all power dependencies of their properties on NA and
that now every Daoud−Cotton blob comprises a 2D self- NB are identical in the regimes of weak and strong adsorption.
avoiding random walk of adsorption blobs rather than The performed generalization demonstrates that several
monomers.35 The relationship between the number of theoretical assumptions adopted in Section II, such as the
monomers g(r) and the size ξ(r) of Daoud−Cotton blobs is strong adsorption approximation and the location of AB
given by junction points strictly at the core−liquid−air triple line, are
1/ + now relaxed while the final conclusions remain unchanged.
ij (r ) yz 2D
When adsorption is sufficiently weak, a finite fraction of
gadsjjj zz
+ + + +
( 3D)/ 1/
g (r ) (r )
j ads zz
2D 2D 2D
corona chains desorb from the interface and swell in liquid to
k { form a 3D corona of the surface micelle. Short-range repulsions
4/3
i zy in the 3D corona are much weaker than in the 2D corona,35 so
1/3j
jr
jj zzz the desorption threshold can be estimated from the free energy
j pz
k { (40) balance between adsorption and short-range repulsions per A
This result generalizes eq 5 to a weak adsorption regime and block in 2D corona, Fads + F2D
corona ≃ 0. The adsorption free energy
reproduces it for δ ≃ 1 when each adsorption blob contains just per one chain is equal to the number of adsorption blobs in it:
one monomer. Eq 40 suggests that each 2D Daoud−Cotton NA 5/3
blob contains δ−1/3 more monomers than in the case of strong Fads NA
adsorption. (Using ϕ ≈ 1/2 would lead to δ−2/5 factor.) gads (48)
According to eq 6, this is simply equivalent to the effective
The energy of 2D excluded volume interactions per corona
shortening of the corona block length compared to the strong
chain in starlike micelles is on the order of their aggregation
adsorption regime
number, Fst,2D 3/4 1/2
corona ≃ pst ≃ γ0 NB , as follows from eq 9. This value
NA NA = ( +
2D
+
3D)/
+
NA =
2D 1/3
NA (41) is much higher than Fcorona ≃ p1/2
st,3D
st for starlike micelle with the 3D
corona,29 which justifies neglecting the latter. One finally arrives
At that, the integral in eq 9 defining the corona free energy as the at the desorption condition given by δstdes ≃ (pst/NA)3/5, in
number of 2D Daoud−Cotton blobs in each A block remains agreement with that for polymer stars with pst arms.35 Using eq
unchanged, and so do the surface and core free energies. 42 yields the threshold
Therefore, all results for micelles with weakly adsorbed corona
3/5
can be obtained from what was found earlier in Section II via i N1/2 yz
st 9/20 3/10 3/20j
jj 0 B zz
corona block length renormalization, NA → Ñ A. NB N A 3/5 jj z
des 0 0 j NA zz
By applying this substitution to eqs 20−22, one can find the k { (49)
properties of starlike micelles
below which desorption becomes significant. The longer the
3/4 1/2
pst 0
NB (42) corona block, the higher the propensity of the micelle to have a
completely flat corona. In contrast, long core blocks and high
1/4 1/2 core surface tension promote aggregation and strengthen short-
R st 0 NB (43)
range repulsions in 2D corona, thereby provoking detachment of
Hst 1/4 3/16 3/4 1/8
NA NB the A blocks from the interface.
0 (44) An analogous estimate can be performed for crew-cut micelles
Here, we used ν = ν+2D
= 3/4, the crossover exponent value of ϕ where the free energy of A blocks in 2D corona equals Fcc,2D
corona ≃
≈ 3/5, and omitted α ≃ β ≃ 1. The adsorption strength δ does γ8/11
0 δ
1/11 3/11 4/11
NA NB . A finite fraction of corona chains leave the
not affect the micelle aggregation number and core radius as interface when the adsorption energy is lower than
repulsions between corona chains in a starlike regime are weak. 6/13
The corona radius goes down with decreasing δ because corona ij N1/2 yz
cc jj 0 B zz
jj z
blocks are less confined to the interface. If the corona radius is des
j NA zz
expressed as the function of the aggregation number (see eq 7), k { (50)

6168 https://doi.org/10.1021/acs.macromol.3c00851
Macromolecules 2023, 56, 6162−6172
Macromolecules pubs.acs.org/Macromolecules Article

Similar to starlike micelles, the corona remains quasi-flat

provided that corona blocks are sufficiently long and/or core
blocks are short.
To conclude, scaling laws derived in Section II are valid not
only for strong adsorption of corona blocks (ensured when 3D
solvent quality is poor) but also for weak adsorption from good/
athermal solvent provided that δ ≥ δstdes and δ ≥ δcc des for starlike
and crew-cut micelles, respectively. For micelles of PS-b-P4VP
and PS-b-PMMA experimentally studied in ref 11, corona blocks
are insoluble in the water bulk and the adsorption expected is
sufficiently strong, i.e., the corona is effectively 2D. In the
experiment, P2VP blocks’ desorption and submerging into the Figure 3. Schematic representation of circular surface micelle with 2D,
disk-like core and 2D adsorbed corona.
water was reported to happen only under very acidic conditions,
pH = 1.8, when monomers become ionized and completely
water-soluble.21,55 In contrast, empirical scaling laws of ref 11 are R (pNB)1/2 (51)
found for neutral pH conditions (pure deionized water) when and differs from the result for the 3D core defined by eq 14. If the
P2VP is nonionized and insoluble in the subphase. core normal height is fixed, aggregation between the core blocks
IV.3. Micellar Polymorphism. How wide the stability does not diminish the area of core−water and core−air
region of crew-cut micelles is defined by the position of the interfaces but diminishes the length of the core−water−air
transition from circular to wormlike morphology. In usual contact line. If the respective line tension at the edge of the 2D
micelles with the 3D corona, the latter is controlled by the core is denoted Γ, the excess surface (line) energy promoting
competition between the core block stretching and the aggregation should be written as
curvature-induced correction to the free energy of repulsions
in a quasi-planar corona. It has been demonstrated that the 2 R NB1/2
region of crew-cut micelle stability in dilute solutions is Fsurf =
p p1/2 (52)
substantial,29,48 in contrast to the case of AB diblock copolymer
bulk where (bcc-packed) micelles are never crew-cut. In this The corona structure for 2D + 2D and 3D + 2D micelles
respect, one can expect that the considered micelles with a coincide and eqs 6−9 remains unchanged. The same applies to
swollen 2D corona are akin to usual 3D micelles in solution. the free energy of the core block stretching, eq 18, which remains
Hence, they should remain crew-cut in a broad range of block negligible compared to the surface (line) and corona repulsions
lengths and exhibit polymorphism at a much shorter length of contributions. Minimization of the total free energy, Ftot(p) ≈
the corona block than that at the starlike/crew-cut crossover Fsurf + Fcorona, with respect to the aggregation number p leads to
given by eq 24. This is consistent with the results of experimental the scaling laws for the physical properties of micelles with 2D
studies, where micelles with as low corona thickness to core core and 2D corona. Starlike 2D + 2D micelles obey
radius ratio as H/R = 0.2 remain circular.11 2/3 1/3
Micellar polymorphism and the transition from crew-cut pst NB (53)
circular to wormlike surface micelles have been experimentally 1/3
reported22,26,46 for Θ and good solvent conditions and should be R st NB2/3 (54)
theoretically examined in the future. This appears challenging as 2(1 )/3
the exact numerical coefficients in eq 18, which defines the core Hst NB(1 )/3
NA (55)
elastic energy,47,48 are unknown when it has a lens-like shape. Similar to the 3D + 2D micelles, their aggregation numbers and
Another complication arises from the fact that the corona free core sizes are independent of NA, but other scaling exponents are
energy is controlled by the linear (not the surface) grafting slightly different, cf. eqs 20−22. Completely flat micelles remain
density of the A blocks while surface energy depends on the starlike if the corona block is longer than
average core surface area per chain. This does not enable
extending an elegant approach of Zhulina et al. from 3D + 3D NAst/cc (2 1)/3
NB(1 + )/3
(56)
solution micelles to 3D + 2D surface aggregates.29,48
As the corona block is shortened, micelles become crew-cut and
V. MICELLES WITH 2D CORE AND 2D CORONA their physical properties are given by
2 /(1 + )
Effectively 3D shape of the surface micelle core was provided by ij yz
the core nonwetting condition, γ1 + γ2 ≳ γ0. Albeit the available pcc jj zz NB
jj N zz
experiments apparently correspond to this case, it is of interest to k A{ (57)
consider the opposite scenario when the core spreads at the /(1 + )
water−liquid interface. If so, the core has a completely planar 2D ij yz
R cc jj zz NB
shape, as shown in Figure 3. The normal height of such a disk- jj N zz
like core does not depend on the r-coordinate and can be k A{ (58)
assumed on the order of the monomer size. For a thicker strictly Hcc (1 )/(1 + ) 2 /(1 + )
NA (59)
2D core, the resulting scaling laws would be the same; this is
similar to strong/weak adsorption regimes of the corona block Numerical values of the scaling exponents for micelles with
discussed in Section IV.2. 2D core and 2D corona can be found using νΘ2D = 4/7 and νΘ2D =
For micellization to take place, the 2D solvent quality for the 3/4 and are summarized in Table 2. Comparison to the results of
core block should be bad. Owing to the core containing no Table 1 reveals a moderate difference in the exponents between
solvent, the radius of the 2D core is equal to 2D + 2D and 3D + 2D micelles. Although the 3D + 2D model
6169 https://doi.org/10.1021/acs.macromol.3c00851
Macromolecules 2023, 56, 6162−6172
Macromolecules pubs.acs.org/Macromolecules Article

Table 2. Theoretical Scaling Laws for Circular Surface Theoretical exponents for 3D + 2D micelles are compared to
Micelles with 2D Core and 2D Coronaa the experimental scaling laws of ref 11. In that work, empirical
exponents were found by numerically fitting the data for any
aggregation corona
regime number, p core radius, R thickness, H circular micelles with a single power law. The most empirical
exponents are in between the limiting theoretical values found in
Θ theory, ∼N0.0
A NB
0.33
∼N0.0
A NB
0.67
∼N0.57
A NB
0.14

solvent starlike the present paper, see Table 1. This is consistent with the
theory, crew- ∼N−0.73
A N1.0
B ∼N−0.36
A N1.0
B ∼N0.73
A NB
0.0 experimentally studied range of micelle morphologies, 0.2 ≤ H/
cut R ≤ 2, corresponding to the crossover between starlike and crew-
+ theory, ∼N0.0
A NB
0.33
∼N0.0
A NB
0.67
∼N0.75
A NB
0.08
cut regimes.
solvent starlike The strength of the corona block adsorption does not alter
theory, crew- ∼N−0.86
A N1.0
B ∼N−0.43
A N1.0
B ∼N0.86
A NB
0.0
theoretical dependencies of the core radius, corona thickness,
cut
a and aggregation number of micelles on NA and NB. Adsorption
Different exponents correspond to starlike or crew-cut morphology
strength δ decreasing below unity is shown to be equivalent to
of micelles and to theta (Θ) or good (+) solvent quality for the
corona blocks. shortening the corona block length by the factor of δ1/3. The
results obtained remain valid until the finite fraction of corona
chains desorb and submerge into the water subphase to form a
with a nonspreading core should better correspond to the 3D corona of the surface micelle.
experimental conditions of ref 11, the exponents obtained from The lens-like, essentially 3D shape of the core is provided by
the 2D + 2D model do not strongly contradict the empirical its nonspreading at the air−liquid interface, and the contact
scaling laws. This result indicates that a flat 2D corona is the angles can be found from the Neumann construction with due
most important feature of surface micelles, while the effect of the regard to the corona contribution to the effective air−liquid
core shape is weaker. surface tension. If the core wets the interface, it acquires a quasi-
For flat 2D + 2D micelles, the boundary between circular 2D disk-like shape. Scaling laws for micelles with 2D core and
crew-cut and wormlike micelles can be found using the method 2D corona are found to differ from those for 3D + 2D aggregates
developed by Zhulina et al. for usual 3D + 3D micelles29,48 not much, thereby illustrating that corona confinement at the
owing to (i) the exactly known numerical coefficients in the air−liquid interface is the key feature of surface diblock
elastic free energies of B blocks in 2D core47 and (ii) the fact that copolymer micelles.
a single variable�linear grafting density of the corona chains
1
= p/2 R �controls both corona and surface contribu-
tions. The formation of wormlike micelles is thermodynamically
■
*
ASSOCIATED CONTENT
sı Supporting Information
advantageous when the corona block becomes shorter than The Supporting Information is available free of charge at
N Acc/w (2 1)/3
NB(1 + )/3 https://pubs.acs.org/doi/10.1021/acs.macromol.3c00851.
(60)
(I) Comparison between scaling laws for micelles with 2D
The calculation details can be found in the Supporting and 3D coronae; (II) derivation of the surface pressure−
Information. Comparing eqs 56 and 60, one can notice that area relationship; (III) core block compression perpen-
Ncc/w
A ≃ Nst/cc
A and the region of crew-cut micelles stability is very dicular to the interface; (IV) transition between circular
narrow, on the order of unity in terms of NA-width. The exact and wormlike micelles with 2D core and 2D corona
width can be found using more rigorous analysis retaining all (PDF)
numerical coefficients. From a scaling point of view, circular
crew-cut 2D + 2D micelles are never stable. At decreasing NA
and/or increasing NB, circular starlike 2D + 2D micelles should
form wormlike aggregates right at the crossover to crew-cut
■ AUTHOR INFORMATION
Corresponding Author
morphology. The fact that the experimentally reported H/R Artem M. Rumyantsev − Department of Chemical and
values are as low as 0.2,11 i.e., micelles are close to the crew-cut Biomolecular Engineering, North Carolina State University,
limit, indicates that the 3D + 2D surface micelle model should be Raleigh, North Carolina 27695-7905, United States;
more appropriate than the 2D + 2D model discussed in this orcid.org/0000-0002-0339-2375; Email: rumyantsev@
section. ncsu.edu
Complete contact information is available at:
VI. CONCLUSIONS https://pubs.acs.org/10.1021/acs.macromol.3c00851
The scaling theory of equilibrium diblock copolymer surface
micelles has been developed. Surface micelles were modeled as Notes
aggregates with 3D lens-like cores and 2D corona adsorbed at The author declares no competing financial interest.
the air−water interface. Power-law dependencies of the micelle
physical properties on the corona and core block lengths, NA and
NB, have been derived for the limits of micelles with small core
■ ACKNOWLEDGMENTS
The author gratefully acknowledges Alexei Kananenka for
but large corona (starlike regime, H/R ≫ 1) and bulky core but bringing ref 11 to his attention and Alexei Gavrilov and Heyi
thin corona (crew-cut regime, H/R ≪ 1). For both regimes, Liang for critically reading the initial manuscript.
micelle aggregation numbers depend on the 2D solvent quality
of the air−water interface for the corona chains. It controls the
strength of their short-range repulsions and is quantified by ν
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Macromolecules 2023, 56, 6162−6172