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Small Angle Neutron Scattering Study of

Conformation of Oligo(ethylene
glycol)-Grafted Polystyrene in Dilute
Solutions: Effect of the Backbone Length
Gang Cheng Yuri B. Melnichenko George D. Wignall

Fengjun Hua Kunlun Hong Jimmy W. Mays

This paper is posted at DigitalCommons@University of Nebraska - Lincoln.

http://digitalcommons.unl.edu/usdoepub/73
 Macromolecules 2008, 41, 9831-9836 9831

Small Angle Neutron Scattering Study of Conformation of

Oligo(ethylene glycol)-Grafted Polystyrene in Dilute Solutions: Effect
of the Backbone Length
Gang Cheng,*,† Yuri B. Melnichenko,† George D. Wignall,† Fengjun Hua,‡
Kunlun Hong,*,‡ and Jimmy W. Mays‡
Neutron Scattering Science DiVision and Center for Nanophase Materials Sciences and Chemical
Science DiVision, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831
ReceiVed June 18, 2008; ReVised Manuscript ReceiVed October 16, 2008

ABSTRACT: The conformation and clusterization of comblike polymers of polystyrene densely grafted with
oligo(ethylene glycol) (OEG) side chains in 1.0 wt % solutions of D2O, toluene-d8, and methanol-d4 was investigated
as a function of the degree of polymerization (DP) of the backbone by small angle neutron scattering (SANS).
Each side chain had four EG repeat units, and the DP of the polystyrene backbone varied from 8 to 85. The
global conformation of the polymers in toluene and methanol was shown to assume ellipsoidal, rigid cylindrical,
or wormlike morphologies with increasing DP of the polystyrene backbone. At the same time, in D2O, the polymer
conformation was described by the form factor of rigid cylinders. The second viral coefficient A2 was measured
for the polymer with a DP of 85 in all three solvents, and the solvent quality of toluene, methanol, and D2O was
identified to be good, marginal, and poor, respectively, for this polymer. Because of a poor solvent quality, the
PS backbone (DP ) 85) is partially collapsed in D2O, whereas it is moderately expanded in toluene and methanol.
Polymers with a DP of 8 were found to form clusters in all three solvents, with the characteristic size between
100 and 200 Å and a fractal dimension of 2. With the increase in the DP, the clusters diminished in D2O and
completely disappeared in toluene and methanol. This observation suggests that the clusterization of these short
side-chain polymers is caused by end-group and hydrogen bonding interactions between different chains.

1. Introduction of the length and composition of the backbone and side chains
to achieve desired structures and functions. A main research
Comblike polymers have received a great deal of attention
activity involves optimization of the properties of OEG-grafted
because of their unique architecture and versatile conforma-
polymers as polymer electrolytes where the OEG side chains
tions.1-10 If side chains are long enough, then the backbone
are good ionic conductors.11,12 Another major thrust has been
becomes highly extended because of the topological stiffness,4
in the biomedical applications in view of nontoxic, nonimmu-
and the global conformation corresponds to that of a wormlike
nogenic properties of EG. It is now widely accepted that the
chain. Theoretical and computer simulation studies have focused
OEG-grafted polymers with hydrophobic backbones have many
on the wormlike chain regime where scaling relations between
advantages over poly(N-isopropylacrylamide) (PNIPAM), a well
the persistence length, the length of the side chains, and the
studied model system in biomedical applications.13-15 By
number of the side chains per backbone repeat unit are predicted;
varying the number of EG repeat unit in the side chain, the
however, many of the theoretical predictions cannot be verified
cloud point temperature (CPT) of their aqueous solutions can
because of the limited amount of experimental data and
be controlled within the physiological range.15
availability of proper comblike polymers.3,5,10d Experimental
investigations by SANS and light scattering (LS) have mainly Information on the conformation properties of OEG-grafted
concentrated on hydrophobic comblike polymers where the polymers at interfaces14,16 and in aqueous solutions under
interactions of backbone and side chains with solvents are not different conditions13,17-19 is required before their applications
significantly different. The global conformation of polystyrene- can be exploited. SANS and LS are complementary techniques,
grafted polynorbornene comblike polymers has been described and both are important in revealing the conformation of the
as compact spheres or cylinders depending on the DP of the polymers in solutions on the length scale on the order of
backbone.9 Combined SANS and computer simulation studies 10-1000 Å (SANS) and 100-10 000 Å (LS), respectively. The
of poly(n-butyl acrylate) grafted poly(alkyl methacrylate) contrast between the polymers and the solvent is defined by
demonstrate that in a good solvent, a side-chain conformation different physical parameters: the neutron scattering length
is close to that of the random coil, the backbone is stretched; density (SLD) for SANS and the refractive index for LS. SANS
and the persistence length increases with the side-chain length has been largely used for the investigation of the conformation
until it reaches a limit.3 Recent SANS investigations on the of the polymers in solution because of the appropriate length
conformation of polystyrene-grafted polymethacrylate show a scales involved as well as the significant contrast between
flexible coil to stiff cylinder transition as the length of the side hydrogenated polymers and deuterium-substituted solvents. We
chains increases.5 previously investigated the conformation of the PS densely
grafted with EG chains at a fixed length of the backbone (DP
OEG-grafted polymers are promising materials for different
) 30) and side chains (DP ) 4) in water using SANS.2 It was
applications owing to the special properties of EG in addition
found that the polymers formed clusters in D2O, whereas they
to the comblike architecture, which allows independent variation
were molecularly dispersed in toluene; the shape of individual
polymers could be described as a short cylinder or an ellipsoid.
* Corresponding authors. E-mail: [email protected] and [email protected]. The major aim of the present work was to study the variation
†
Neutron Scattering Science Division.
‡
Center for Nanophase Materials Sciences and Chemical Science of the polymer conformation as a function of the DP of the
Division. backbone (DP ) 8, 40, 47, 58, 85) and fixed length of the side
10.1021/ma801370q CCC: $40.75  2008 American Chemical Society
Published on Web 11/25/2008
This article is a U.S. government work, and is not subject to copyright in the United States.
9832 Cheng et al. Macromolecules, Vol. 41, No. 24, 2008

c P(q)
I(q) ) + bkg (1)
K 1 + 2cA M P(q)
2 w

where c is the concentration in g/mL, Mw is the weight-average

molecular weight, K ) VpF ⁄∆F2Vp2, F is the mass density of a
polymer, ∆F is the SLD difference between the polymer and
solvent, Vp is the volume of one polymer, and bkg is the incoherent
Figure 1. Chemical structure of PTrEGS. n is the DP of the backbone.
scattering from the polymers. A2 is the second virial coefficient
that characterizes the average interactions between two polymers
EG chains (DP ) 4) in various solvents (toluene-d8, methanol- in infinitely dilute solutions, P(q) is the form factor, and P(q ) 0)
d4, and D2O). One set of experiments was performed at fixed ) 1. Assuming a Schulz distribution of the particle sizes22
polymer concentration (1.0 wt %) and variable DP, and the
global conformation of the polymers was assessed in all three rz z + 1 z+1 -r(z + 1)
solvents by fitting the SANS data to form factors of rigid or
semiflexible cylinders (wormlike chains). Another set of experi-
f(r) )
Γ(z + 1) <r> ( exp ) <r>[ ] (2)

ments was designed to study SANS from polymer solutions with The polydispersity σ is given as σ2 ) 1/(z + 1).
The averaged form factor is then given as
fixed backbone length (DP ) 85) as a function of the polymer
concentration in the range of 0.2 to 1.0 wt %. These data were
used for determining the second virial coefficient in toluene- P(q) ) ∫ P(q)V f(r) dr ⁄ ∫ V f(r) dr
2
p
2
p (3)
d8, methanol-d4, and D2O to identify the solvent quality. Our When 2cA2Mw , 1, eq 1 is reduced to22
studies revealed a strong influence of the end groups on the
clusterization of the short-chain polymers in all studied solvents. 
I(q) ) (∆F)2V2pP(q) + bkg (4)
2. Experimental Section Vp
2.1. Materials. The chemical structure of the homopolymer where  ) c/F is the volume fraction of the particles.
(abbreviated PTrEGS) is shown in Figure 1. The DP of the polymers The A2 value was determined via the Zimm plot, c/I(q ) 0)
is 8, 40, 47, 58, and 85, and the polydispersity index is <1.3, both versus c
determined by gel permeation chromatography. The density of the
c
backbone is assumed to be that of PS, 1.05 g/cm3, and that of the ) K(1 + 2A2cMw) (5)
side chain is assumed to be that of PEG, 1.12 g/cm3. The polymers I(0)
were mixed with the solvents and kept for 24 h at room temperature The SLD of the PS is 1.4 × 10-6 Å-2, and that of the EG is
before the measurements. 0.62 × 10-6 Å-2. The contrast between D2O (6.4 × 10-6 Å-2) and
2.2. SANS Measurements. SANS measurements were per- each of the component polymers is similar; therefore, SANS detects
formed at different neutron facilities: the Institute of Materials the global conformation of the polymer.
Research at GKSS, Germany; NCNR at the National Institute of
Standard and Technology; and General Purpose SANS instrument 3. Results and Discussion
(SANS-I) at the HFIR Center for Neutron Scattering at Oak Ridge 3.1. Solvent Quality for PTrEGS with a DP of 85. The
National Laboratory.
solution properties of PEG (or poly(ethylene oxide)) in water
The experiments at NIST were performed on the NG3 30m
instrument20a with a neutron wavelength of λ ) 6.0 Å (∆λ/λ ≈
have been extensively investigated. PEG molecules often form
0.15). Two sample-detector distances were used (1.5 and 13.0 m clusters in water, and the origin of this clusterization has not
with a 25 cm detector offset), which leads to an overall q range of been completely understood.24,25 Nevertheless, water has been
0.0038 Å-1 < q ) 4πλ-1 sin θ < 0.40 Å-1, where 2θ is the described as a good solvent for PEG homopolymers.26 In the
scattering angle. The data were corrected for instrumental back- presence of the hydrophobic PS backbone, the distribution of
ground as well as detector efficiency and were put on absolute scale water molecules around PEG side chains is strongly perturbed,
(cross section I(q) in units of cm-1) on the basis of the direct beam and their solubility in water is expected to drop. In fact, it takes
flux method. Scattering from the solvent was subsequently sub- more than 10 h to dissolve 1.0 wt % PTrEGS in D2O, and the
tracted in proportion to its volume fraction. CPT of this solution (∼38 °C) is significantly lower than that
The experiments at ORNL were performed on the SANS-I instru- of aqueous solutions of PEG (above 100 °C25). The CPT of
ment (http://neutrons.ornl.gov/hfir_instrument_systems/CG-2.shtml) 1.0 wt % H2O solution of DP ) 85 is ∼40 °C because of the
with a neutron wavelength of λ ) 4.8 Å (∆λ/λ ≈ 0.14). Two better solubility of the polymers in H2O. It is believed that the
sample-detector distances were used (2.8 and 16.8 m with a 40 cm solvation of the PTrEGS polymers in water is similar to that of
detector offset), which resulted in the overall q range of 0.0045 Å-1 protein globules in which the hydrophobic core is surrounded
< q ) 4πλ-1 sin θ < 0.45 Å-1. The data were corrected for by a shell of hydrophilic segments.27 The PTrEGS polymers
instrumental background as well as detector efficiency and were put are readily dissolved in toluene because of strong interactions
on absolute scale (cross section I(q) in units of cm-1) by means of between PS backbones and toluene molecules. Methanol
precalibrated secondary standard.20b Scattering from the solvent was molecules have both hydrophilic hydroxyl groups and hydro-
subsequently subtracted proportionally to its volume fraction. phobic methyl groups; therefore, the PTrEGS polymers can also
The experiments at GKSS were performed on the SANS-2
be easily dissolved in methanol.
instrument (http://www.gkss.de/central_departments/genf/instruments/
003124/index_0003124.html.en) with a neutron wavelength of λ )
Figure 2 shows the SANS data of 1.0 wt % polymers with
5.8 Å (∆λ/λ ≈ 0.10). Two sample-detector distances were used (0.8 DP ) 85 in toluene-d8, methanol-d4, and D2O. Within the q
and 3.8 m), which leads to an overall q range of 0.0080 Å-1 < q ) range investigated, SANS data show no signs of the polymer
4πλ-1 sin θ < 0.30 Å-1. The data were corrected for instrumental clusterization in all three solutions. To characterize the solvent
background as well as detector efficiency and put on absolute scale quality, the A2 values of this polymer were determined in all
(cross section I(q) in units of cm-1) on the basis of a standard sample three solvents by Zimm analysis (eq 4).
of a single crystal of vanadium. Scattering from the solvent was The values of I(0) were obtained from SANS data in the
subsequently subtracted proportionally to its volume fraction. concentration range of 0.2 to 1.0 wt % via Guinier analysis.
The measured neutron scattering intensity in dilute solutions per The maximum polymer concentration (1.0 wt %) was much
unit volume is expressed as21 lower than the overlap concentration (∼8.3 wt %) estimated
Macromolecules, Vol. 41, No. 24, 2008 SANS Study of OEG-Grafted Polystyrene 9833

Figure 2. SANS curves of 1.0 wt % PTrEGS homopolymers with DP

) 85 in D2O (data taken at ORNL), toluene-d8, and methanol-d4 (data
taken at NIST).

Figure 3. Zimm plot for the polymers with a DP of 85 in three solvents.

via c* ) Mw/NAV, where V ) (4πRg3)/3, NA is Avogadro’s

number, and the radius of gyration Rg ) 55 Å was obtained
from Guinier analysis of the data of 0.2 wt % toluene solution.
Zimm plots for PTrEGS solutions in all three solvents are
shown in Figure 3. The obtained values of A2: (5.0 ( 1.6) ×
10-4 mol · cm3 · g-2 (toluene-d8), (1.4 ( 1.8) × 10-4
mol · cm3 · g-2 (methanol-d4), and -(4.2 ( 1.1) × 10-4
mol · cm3 · g-2 (D2O) allow us to categorize the solvent quality
of toluene-d8, methanol-d4, and D2O for PTrEGS as good,
marginal, and poor, respectively. The negative A2 value of Figure 4. SANS curves of 1.0 wt % PTrEGS homopolymers with
PTrEGS in D2O, which is in contrast with positive values of different DPs of the backbone in (a) toluene-d8, (b) methanol-d4, and
(c) D2O. For the sake of clarity, the data of the toluene solutions were
PEG in water,26 suggests that the interactions between the shifted by a factor of 1.2, 4, 8, 14, and 24 for the polymers of DP )
polymers in this solvent are attractive, and this is attributed to 8, 40, 47, 58, and 85, respectively. The data of the methanol solutions
insolubility of hydrophobic PS backbones in water. Individual were shifted by a factor of 6, 12.5, 22, and 30 for the polymers of DP
homopolymers such as PS are known to collapse into globules ) 40, 47, 58, and 85, respectively. The data of the D2O solutions were
shifted by a factor of 0.8, 5.7, 16, 32, and 90 for the polymers of DP
in poor solvents, and the globules tend to form clusters because ) 8, 40, 47, 58, and 85, respectively. The inset in a shows the schematic
of attractive interactions between polymer segments.27,28 The diagram of the shape transition of the polymers with increasing DP.
absence of clusters in the aqueous solution of the PTrEGS (DP The solid lines are fits to different models, as described in the text.
) 85) is probably due to the availability of the water-soluble 3.2. Polymer Conformation and Clusterization in 1.0
EG side chains, which stabilize the solubility of PTrEGS in wt % Solutions. To investigate the influence of the DP of the
D2O.27 However, with the decrease in the DP, as will be backbone on the conformation of the PTrEGS polymers, we
discussed later, other factors start to dominate the clusterization. measured SANS from 1.0 wt % polymer solutions with DP )
The nearly zero A2 suggests that the solubility of the polymers 8, 40, 47, 58, and 85 in toluene-d8, methanol-d4, and D2O. (See
in methanol is between toluene and D2O. The molecular weight Figure 4.) A striking feature is that the polymers with a DP of
of the polymer, Mw, determined from Zimm plots in toluene-d8 8 formed clusters in all three solvents. The clusters were also
(27 800 g/mol), methanol-d4 (39 600 g/mol), and in D2O (29 000 detected in 0.1 wt % toluene solution (data not shown). They
g/mol) agrees within 20% with the Mw measured using gel were not observed within the experimental window in both
permeation chromatography (34 800 g/mol). toluene-d8 and methanol-d4 for polymers with a DP of 30 (ref
9834 Cheng et al. Macromolecules, Vol. 41, No. 24, 2008

2), 40, 47, 58, and 85; in D2O, the clusterization gradually Table 1. Fitted Parameters for Polymers in D2O, Toluene-d8, and
diminished with the increasing DP. Because the chemical Methanol-d4
composition of the PTrEGS polymer remains unchanged with Polymers in D2O
DP, it appears that the observed DP-dependent clusterization is
induced by interactions between the end groups of the PTrEGS DP L (Å)a R (Å)b σc
polymers as the relative concentration of the end groups drops 85 136.2 ( 0.5 13.3 ( 0.1 0.27 ( 0.01
with the increase in the DP. In addition, the probability of the 58 106.2 ( 0.3 14.1 ( 0.1 0.22 ( 0.01
end-group interactions drops with increasing DP because of the 47 88.0 ( 0.2 14.6 ( 0.1 0.15 ( 0.01
40 76.2 ( 0.3 14.9 ( 0.1 0.09 ( 0.01
larger number of conformations available for longer chains.
L (Å) R (Å) S (0)d  (Å)e
The A2 value is related to the interactions between polymers in 8 65.2 ( 0.3 16.3 ( 0.1 12.5 ( 0.2 196.1 ( 1.6
solution. It is known to be molecular-weight dependent,26,30 and
Polymers in Toluene-d8
the dependence may be altered by the chemical composition of
the end groups.24,29 As shown in Figure 1, each PTrEGS DP L (Å) R (Å) σ b (Å)f
polymer is terminated by a hydrophobic phenyl group on one
85 238.5 ( 0.9 10.5 ( 0.1 0.30 ( 0.01 82.7 ( 1.0
end and a bromine atom on the other end. The insoluble 58 133.1 ( 1.0 10.8 ( 0.1 0.30 ( 0.01 82.7 ( 1.0
hydrophobic end groups tend to avoid contacts with D2O 47 81.8 ( 0.5 11.6 ( 0.2 0.30 ( 0.01
molecules and try to interact with the hydrophobic end groups 40 60.6 ( 0.4 12.6 ( 0.1 0.24 ( 0.01
of other molecules. The probability of end-to-end interactions Ra (Å)g Rb (Å)h S (0)d  (Å)e
becomes lower with increasing DP because of the mentioned 8 23.9 ( 0.6 11.8 ( 0.1 0.7 ( 0.1 102.9 ( 2.7
reasons. This is consistent with computer simulations,24 which Polymers in Methanol-d4
indicate that the attractive interactions increase with the decrease
in the molecular weight because of the presence of the DP L (Å) R (Å) σ b (Å)f
hydrophobic end groups in aqueous solutions of methyl- 85 220.3 ( 1.7 11.7 ( 0.1 0.27 ( 0.01 71.2 ( 1.3
terminated PEG. In addition to the above-mentioned end-to- 58 139.9 ( 0.7 11.6 ( 0.2 0.24 ( 0.01 71.2 ( 1.3
end interactions, the hydrophobic end groups may also interact 47 76.6 ( 0.4 12.1 ( 0.1 0.26 ( 0.01
40 60.1 ( 0.3 12.5 ( 0.1 0.20 ( 0.01
with methyl end groups of EG side chains of other polymers, Ra (Å)g Rb (Å)h S (0)d  (Å)e
and this type of interaction is shown to be responsible for 8 31.3 ( 0.4 10.4 ( 0.1 1.4 ( 0.1 151.8 ( 1.6
clusterization of PEG in water.25 Finally, the clusterization may a
Length of a cylinder. b Cross-section radius of a cylinder. c Polydis-
be further facilitated by attractive interactions between EG side persity of R. d Related to the susceptibility of the solutions. e Characteristic
chains via hydrogen bonding,24 where D2O molecules act as length of the clusters. f Kuhn length of a semiflexible cylinder. g Rotational
the physical cross-linkers between side chains that belong to semiaxis of an ellipsoid. h Another axis.
different polymers. Currently, we do not have a convincing
explanation of the observed polymer clusterization in good and
D2O were not possible because of the strong contribution of
marginal solvents (toluene and methanol). However, we note
that the clusterization in polymer solutions is a common scattering from clusters. However, it is expected that the effect
phenomenon and was previously documented in polymer of A2 on the fitted cylinder volumes of other polymers with
solutions such as PS in cyclohexane around the θ temperature.31 lower DP will be within ∼20%.
Figure 4a,b shows the SANS patterns from the PTrEGS The data presented in Table 1 show that the dimensions of
polymers in toluene and in methanol, respectively. The solid the cylinders or semiflexible cylinders decrease with the DP.
lines on the SANS curves are fits to eq 4. When the backbone For DP ) 85 and 58, the polymer backbone is in a folded27 or
length is larger than the persistence length of the polymer, the crumbled33 state in the poor solvent D2O in contrast with that
polymer conformation is better described by the form factor of in toluene and methanol. This conclusion is not affected by the
a semiflexible cylinder. On the contrary, when the backbone finite concentration effect because it tends to overestimate
length is smaller than the persistence length, the conformation
the dimensions of the polymers in D2O and underestimate the
is better described by the form factor of a rigid cylinder. For
dimensions in toluene and methanol. Further collapse of this
polymers with DP ) 85 and 58, a form factor of the semiflexible
cylinder32 (eq A3 in the Appendix) was used, and the rigid polymer in D2O is expected at higher temperatures,2 which is
cylinder form factor (eq A1 in the Appendix) was chosen for consistent with the proposed multistep chain collapse during
DP ) 47 and 40. We found that the introduction of an additional the coil-to-globule transiton,27,33 whereas for DP ) 47 and 40,
fitting parameter, polydisperse cross-section radius, was neces- the resulted dimension of the polymers in D2O is comparable
sary to improve the fits. The reduced 2 of the fitting was about to or larger than that in toluene and methanol, which is due to
2 to 3. finite interactions in the solutions and possible aggregation of
The SANS data from the polymers with DP of 85, 58, 47, a fraction of polymers in D2O due to strong end-group
and 40 in D2O (Figure 4c) were consistent with the form factor attractions.27 As will be demonstrated below, the end-group
of the rigid cylinder. The reduced 2 of the fitting was about 3 interactions facilitate the formation of the polymer dimers in
to 5. Because of the nonzero values of the second virial aqueous solutions of short polymer chains with DP ) 8. We
coefficient, the values of fitting parameters presented in Table note that there are some differences between the polydispersity
1 are expected to be concentration dependent. The related of the cross-section radius of the polymers in toluene, methanol,
corrections to the value of the polymer dimensions depend on and in D2O, which can be explained as being due to the
the value of the term 2cA2Mw; positive A2 should lead to an relatively sharp interface between the polymer and the solvent
increase in the fitted dimensions of the polymers, whereas in D2O27 as opposed to a rather diffuse interface in toluene and
negative A2 should result in a reduction in the dimensions. For methanol solutions.
example, when A2 ) -(4.2 ( 1.1) × 10-4 mol · cm3 · g-2 was
included in the fitting (eq 1) of the data from 1.0 wt % polymers The data of the polymer with DP ) 8 were fitted to a
(DP ) 85) in D2O, a ∼20% reduction in the fitted average phenomenological equation combining a form factor character-
volume of the cylinders was observed. Unfortunately, systematic izing individual polymers and a term describing the scattering
measurements of A2 for lower-molecular-weight polymers in from clusters34
Macromolecules, Vol. 41, No. 24, 2008 SANS Study of OEG-Grafted Polystyrene 9835

I(q) )
(∆F)2 2
Vp
VpP(q) +
S(0)
{1 + [(D + 1)/3]2q2}D/2
(6) P(q) ) ∫0
π/2
[ 2j0(qH cos R)
J1(qR sin R) 2
qR sin R ]
sin R dR (A1)

Here  is the characteristic size of the cluster, D is the fractal where Vcyl ) πR2L, H ) L/2, j0(x) ) sin x/x, and J1 is the first-
dimension of the cluster, and S(0) is proportional to the order Bessel function.
2) The form factor of an ellipsoid with axes ra and rb is given
susceptibility of the system.
as23
It was found that an ellipsoid form factor (eq A2 in the
Appendix) best described the scattering curves from toluene and φ
∫ F [qr (1 + x (ν
1
methanol solutions and a rigid cylinder form factor agreed with P(q) ) (F - Fsolv)2
2 2 2
- 1))1/2] dx
Vell ell 0 b
the data from the polymer solutions in D2O. The reduced 2 of
(A2)
the fitting was about 2. The mass fractal dimension of the
clusters is around 2. The obtained dimension of one ellipsoid where
in toluene and methanol is comparable to that of an individual
polymer, the contour length of the PS backbone of which is sin z - z cos z 4π ra
estimated to be 8 × 2.5 ) 20 Å. The obtained contour length F(z) ) 3Vell , Vell ) rar2b, V )
z3 3 rb
of the polymers includes both the length of the PS backbone
and the contributions of the EG side chains near the chain end 3) The form factor of a semiflexible cylinder with the contour
of the backbone.10d The length of the cylinder in D2O (L ) 65 length L e 4b, where b is the Kuhn length, and a cross-section
Å, Table 1) is about 2 times that of one polymer chain if one radius R is given as follows32
takes into account the contributions from the side chains near P(q, L, b) ) Pchain(q, L, b)[2J1(qR)/(qR)]2 (A3)
the end group. We speculate that this dimension corresponds
to the length of smaller aggregates, which consist of about two For qb e q0 (L, b), where q0 ) max{1.9/(<Rg2>1/2), 3}
polymers linearly connected because of end-to-end interactions,
as suggested by the computer simulation.27 Pchain(q, L, b) ) 2[exp(-u) + u - 1]/u2 (A4)
where
Summary
u ) R2gq2, Rg ) 〈R2g 〉1/2, 〈R2g 〉 ) R(L/b)2〈R2g 〉0 ,
SANS data demonstrate that the DP of the backbone is a
key factor in controlling the structure of amphiphilic comblike R(x)2 ) [1 + (x/3.12)2 + (x/8.67)3]0.170/3 ,

[ ]
PTrEGS polymers in various solvents. With the increasing DP
Lb 3 3 3
of the backbone, the initially rigid polymers start to behave as 〈R2g 〉0 ) 1– + - [1 - exp(-2nb)] , nb ) L/b
flexible chains, the persistence length of which is mainly 6 2nb 2n2 4n3
b b
determined by the solvent-mediated interactions between EG
For qb > q0(L, b)
side chains. The influence of the end groups on polymer-polymer
interactions becomes especially pronounced at small DPs, that a1 a2 π
is, high relative concentration of end groups, especially in poor Pchain(q, L, b) ) + + (A5)
(qb) p1
(qb) p2 qL
solvents like D2O. As a result, clusterization gradually progresses
in the D2O solutions of PTrEGS polymers with decreasing DP. where p1 and p2 are empirical constants and p1 ) 5.36 and p2 )
Strong clustering is observed in all three solvents for polymers 5.62. a1 and a2 are given in ref 32.
with a DP of 8, and the sizes of the clusters are between 100
and 200 Å. The hydrophobic PS backbone of the polymers (e.g., References and Notes
DP ) 85 and 58) is in a partially collapsed state in D2O, whereas
it expands in toluene and methanol. SANS data also suggest (1) Bolisetty, S.; Airaud, C.; Xu, Y.; Müller, A. H. E.; Harnau, L.;
that the individual polymers assume the shape of a rigid cylinder Rosenfeldt, S.; Lindner, P.; Ballauff, M. Phys. ReV. E 2007, 75,
040803.
with a relatively sharp interface in D2O and with a rather diffuse (2) Cheng, G.; Melnichenko, Y. B.; Wignall, G. D.; Hua, F.; Hong, K.;
interface in toluene and methanol. Mays, J. W. Polymer 2007, 48, 4108.
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AC05-00OR22725 with Oak Ridge National Laboratory, managed (8) Elli, S.; Ganazzoli, F.; Timoshenko, E. G.; Kuznetsov, Y. A.; Connolly,
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