This is an open access article published under an ACS AuthorChoice License, which permits

copying and redistribution of the article or any adaptations for non-commercial purposes.

Letter

pubs.acs.org/macroletters

Stable Freestanding Thin Films of Copolymer Melts Far from the

Glass Transition
T. Gaillard,† C. Poulard,† T. Voisin,†,‡ C. Honorez,† P. Davidson,† W. Drenckhan,*,† and M. Roché†,§
†
Laboratoire de Physique des Solides, CNRS UMR 8502 and Université Paris Sud, Bâtiment 510, 91405 Orsay Cedex, France
*
S Supporting Information

ABSTRACT: Thin polymer films have attracted attention

because of both their broad range of applications and of the
fundamental questions they raise regarding the dynamic response
of confined polymers. These films are unstable if the temperature
is above their glass transition temperature Tg. Here, we describe
freestanding thin films of centimetric dimensions made of a comb
copolymer melt far from its glass transition that are stable for
more than a day. These long lifetimes allowed us to characterize
the drainage dynamics and the thickness profile of the films.
Stratified regions appear as the film drains. We have evidence that
the stability, thinning dynamics, and thickness profile of the films
result from structural forces in the melt. Understanding the key
mechanisms behind our observations may lead to new developments in polymeric thin films, foams, and emulsions without the
use of stabilizing agents.

thin polymer films, the films we study are characterized by

M any industrial and natural processes rely on the dynamic
response of liquids confined to submicrometer dimen-
sions. Examples include coating devices, foams, emulsions or
lifetimes on the order of 1 day, while reaching thicknesses on
the 10 nm scale. Besides their phenomenal stability, these films
lung airways. 1 Confinement can occur in “supported” display a stratified thickness profile. We discuss the mechanism
conditions on a solid surface or in “freestanding” conditions that may explain the stratification of these films as well as their
in which the liquid is confined by two free interfaces. resistance to rupture. We show that the former originates most
Confinement effects become important when the distance likely from structural forces in the liquid that could also explain
between two interfaces separating the liquid from its environ- the stability of the films.
ment is commensurate with a characteristic length scale of the We used a commercially available comb-copolymer (DBP-
liquid; the dynamics of the liquid may then change 732, Gelest Inc., molecular weight Mw ≈ 20000 g·mol−1,
dramatically.2 For example, thin films of complex fluids with polydispersity index = 5) that is molten at room temperature
thickness h < 100 nm can have stratified thickness profiles and at least 60 °C above its glass transition temperature (Figure
whose stratum height is either correlated to the size of the S1 in Supporting Information). The copolymer consists of a
molecules, as in the case of smectic liquid-crystalline films,3−5 poly(dimethylsiloxane) (PDMS) backbone with approximately
or to the characteristic dimensions of aggregates/meshes Nb = 110 siloxane groups of which 27 carry statistical
formed by molecules in solution.6−10 Another manifestation poly(ethylene glycol)/poly(propylene glycol) (PEG/PPG)
of confinement effects is the dependence of the glass transition copolymers (Figure 1a). The side chains are Ns = 10 units
temperature Tg of polymeric materials on film thickness h.11 long (x = 4 PEG units and y = 6 PPG units on average), CH3-
The response of polymeric materials to confinement has
terminated, and connected to the backbone by a (CH2)3 group.
been investigated mostly in the supported case for thicknesses h
We measured the rheological properties of the melt using an
< 100 nm (see ref 12 for a review). Besides a better
Anton Paar MCR 301 rheometer with the cone−plate
understanding of the relationship between Tg and h, questions
such as the stability of thin polymer films against dewet- geometry. Rotational tests showed that the melt viscosity is
ting13−15 or the structuration of block copolymers were constant, η = 2.7 Pa·s, over the range of shear rates 0.1 < γ̇ <
tackled.16−18 In contrast, studies of freestanding thin polymer 1000 s−1 (Figure S2 in Supporting Information).
films are scarce,12,19−25 more so in the case of copolymers.26,27 Vertical thin films of DBP-732 are formed at room
Like their supported counterparts, the stability of these films temperature using a square 30 mm wide frame made of a
decreases as the temperature increases well above Tg. 160 μm thick nylon fiber frame held inside a metal structure
Here we describe observations made for freestanding thin
polymer films of submicrometer thickness drawn from silicone- Received: August 1, 2015
based, comb-like copolymer melts far from their glass Accepted: September 15, 2015
transition. In contrast to the hitherto studied freestanding Published: October 2, 2015

© 2015 American Chemical Society 1144 DOI: 10.1021/acsmacrolett.5b00535

ACS Macro Lett. 2015, 4, 1144−1148
ACS Macro Letters Letter

Figure 1. (a) Molecular structure of DBP-732. x and y denote the numbers of PEG and PPG units in the side chains, respectively. (b) Sketch of the
pulling film setup. L = w = 30 mm. (c) Image of a vertical thin liquid film of DBP-732, t = 1800 min.

Figure 2. (a) Monochromatic image sequence of a vertical DBP-732 film taken at λ = 660 nm. (b) Time evolution of film along purple line on image
a at t = 60 s. z = 0 is taken as the top of the film. (c) Film thickness h vs time t at z = 6 mm under the top nylon fiber (mean over the white disk on
image a, t = 60 s).

(Figure 1b), in analogy to Mysels’ historic soap film thickness h has finally decreased to a few tens of nm. In this
experiments.28 The film is entirely pulled out of a vessel region, the film is stratified (Figure S3 in Supporting
containing the melt at constant velocity U = 5 mm·s−1 and then Information) much like other complex-fluid thin films.6−10
left to drain after removal of the vessel. Figure 1c shows an We found the height of strata to be multiples of Δhv = 16 ± 1
image of a DBP-732 film after 30 hours. Colors result from the nm. We sometimes observe stratification in regions whose
interference pattern of white light reflected at normal incidence thickness is on the order of 500 nm.
by the film. Reflected light is analyzed to extract thickness maps Figure 2b shows that the vertical thickness profiles of DBP-
by collecting it sequentially with three narrow band-pass filters 732 evolves with time like the profiles of vertical soap films
(λ1 = 450 nm, λ2 = 550 nm, λ3 = 660 nm) and processing the draining under gravity.28,33,34 We investigated the ability of
acquired signals using a MatLab code based on Scheludko’s existing soap-film drainage models to capture the thinning
microinterferometric method.29,30 dynamics h(z,t) we observed. First, the long lifetime of the films
DBP-732 films remain stable over time scales on the order of led us to test Reynolds’ drainage model with rigid interfaces28,35
105 s, allowing us to study their drainage dynamics. Figure 2a that predicts the evolution
shows a typical image sequence taken at λ = 660 nm over a
duration of 1600 min after the film has been pulled out (see h0
h(z , t ) =
also Movie M1 in Supporting Information). While the film is 1 + (4/3)α(z)(t − t0) (1)
initially quite smooth (Figure 2a, t = 60 s), recirculation flows
grow across the whole film, and a flow along the vertical nylon with α = ρgzh20/ηL2, ρ the density of the liquid, g the
fibers brings liquid from the bottom of the film to its top gravitational acceleration, z the position on the film, h0 the
(Figure 2a, t = 2 × 103 s and 3 × 104 s). Such flows are often initial thickness at time t0, η the viscosity of the liquid, and L
indications of the presence of surface tension gradients,31,32 but the height of the film. Figure 2c shows that a fit of eq 1 to the
we have no proof of such an assumption yet for this system. As experimental data for h(z,t), with the initial thickness equal to
drainage progresses, recirculating flows vanish, and the top of the thickness of the film right after the removal of the vessel, h0
the film becomes smooth (t = 105 s). Common black films = 447 nm, and α as an adjustable parameter works very well.
grow at the top of the film long before bursting: the film However, the value we obtained for α suggests that η ∼ 10−3
1145 DOI: 10.1021/acsmacrolett.5b00535
ACS Macro Lett. 2015, 4, 1144−1148
ACS Macro Letters Letter

Figure 3. (a) Image sequence of a horizontal draining film. (b) Film thickness profiles along the yellow line on image a, t = 0 s. (c) Thickness
distribution across horizontal films. The hi values indicate the h-value that corresponds to the peaks. Data acquired on five films under identical
experimental conditions. (d) Thicknesses of the strata that appear simultaneously on horizontal films (TFB1 and TFB2) and on vertical films.

Pa·s, a value that is at least 3 orders of magnitude smaller than occurrences, and a linear fit to the data shows that the average
the bulk viscosity of the liquid we measured. The opposite height difference between two strata in both types of films is Δh
situation of drainage between free interfaces is also unable to ≈ 16 ± 1 nm (Figure 3d). Similar observations have been
capture the trends that we report, as the thinning dynamics we reported for thin films of almost glassy diblock copolymers
observe is not exponential.33 This last result also highlights the when film thickness becomes commensurate with the molecular
fact that viscous resistance linked to a high bulk viscosity does size.26,40
not explain the long lifetime of the films, in contrast with thin We investigated the bulk molecular features of the copolymer
polymer films made of very viscous silicone oils36 (η = 103 Pa·s using small-angle X-ray scattering (SAXS) performed on the
in the latter case compared to η = 2.7 Pa·s here). Thus, simple SWING beamline at the SOLEIL synchrotron radiation facility
thin-film drainage models are unable to rationalize the (λ = 1.08755 Å, sample−detector distance 1 m, Saint-Aubin,
dynamics of our films and one may have to resort to more France). We observed an isotropic scattering motif for DBP-
complex models taking into account specific interfacial48 or 732 (Figure 4a and inset) with a peak at a scattering vector qc =
bulk effects. As film thicknesses are larger than 100 nm during 0.040 ± 0.007 Å−1 that indicates a bulk characteristic length lc
most of the drainage process, we expect DLVO forces between ≈ 15.7 ± 2.7 nm similar to the stratum height Δh = 16 ± 1 nm
the interfaces to be negligible. The observation of stratification that we reported earlier. Pattern isotropy is consistent with the
suggests that structural forces may exist in DBP-732 that may absence of a measurable signal when performing birefringence
affect thin-film dynamics. analysis on the sample.
We investigated the existence of structural forces using
Comparison with a theoretical estimate of the size of the
horizontal films that we studied using a thin-film pressure
comb polymer gives an indication of the nature of lc. The
balance37−39 designed to work with viscous fluids. Thickness
macromolecular conformation of branched polymers depends
measurements are performed as in the case of vertical films. At t
on the polymerization degrees Nb and Ns of the backbone and
= 0 the pressure difference between the liquid and the
surrounding nitrogen is increased to 103 Pa. Figure 3a shows side chain, respectively, and on the number of backbone units n
images of the film during its thinning, indicating that the between consecutive side-chain grafting points. We are in the
drainage process may be divided into two stages. During the limit of short non-Gaussian side chains (Ns < 100)41,42 and of a
first stage, the film thickness is inhomogeneous and varies Gaussian backbone.43 The spacers ls between branching points
smoothly across the film (Figure 3a, t = 0 s). When the film are approximately four siloxane units long on average, that is, ls
reaches thicknesses on the order of 70 nm, strata appear at the ≈ 1.3 nm considering that the distance between two silicon
boundaries between well-defined zones of constant thickness atoms in the backbone is given by 2lSi‑O, with lSi‑O = 0.164 nm44
(Figure 3a, t = 600, 1500, and 2400 s). As thinning progresses, and assuming that the monomers are linearly arranged. In
strata appear all over the film and the liquid drains out of the comparison, the non-Gaussian side chains have an approximate
film layer by layer (Figure 3b). The minimum thickness of the full-extension length lsc ∼ 4.5 nm.45 As a consequence, the side
film before breakup is hmin ∼ 30 nm, and we never observed chains see each other and they minimize their interactions by
black films with h < hmin even close to bursting. This is in forcing the backbone to stretch. Thus, we hypothesize that the
contrast with the vertical film, where hmin ∼ 16 nm. A statistical copolymers form dense combs.41,42 Moreover, since we
treatment of the thickness maps of both vertical and horizontal consider melt properties, we assume that individual chains are
films, shows peaks in the distribution of thicknesses (Figure in a θ-solvent. Assuming that only steric interactions matter in
3c). These peak values were reproducible over many film setting the macromolecular conformation42 and neglecting
1146 DOI: 10.1021/acsmacrolett.5b00535
ACS Macro Lett. 2015, 4, 1144−1148
ACS Macro Letters Letter

The occurrence of stratification in freestanding copolymer

films is known to be related to an increase in film stability.27 In
their study, Croll and Dalnoki-Veress suggest that the layered
structures formed by some copolymers when confined in
freestanding films increase the resistance of these films to
thermal fluctuations and DLVO interactions when compared to
other homo- and copolymers that do not organize. DBP-732
might show excellent stability for similar reasons, especially
since the thickness of the film reaches a minimum value hmin ∼
16 nm that would limit the importance of short-range and
thermal fluctuations.
In conclusion, we described the ability of a comb-like
copolymer melt far from its glass transition temperature to
form day-long stable thin films. We discuss the drainage of
these films and identify structural forces in the copolymer melt
as the origin of both stratification and potentially the long
lifetime of the films. Many questions remain open, such as the
role of chain flexibility, molecular structure (backbone and side-
chain lengths, chemical composition of the side chains, etc.),
and the exact organization of the polymers at the interface in
the film. Preliminary results indicate that similar copolymers
with 10−20 units in the backbone are unable to form stable
films. Thus, molecular structure is a crucial parameter and its
Figure 4. (a) SAXS scattering intensity in the bulk of DBP-732. The control would allow tuning the stability of thin copolymer films
black experimental dots are angular averages of all the radial intensity far from their glass transition. Future work also needs to
profiles seen on the scattering image (inset). (b) Suggested structure elucidate the dynamic properties of the polymer/air interface
of the film as drainage proceeds. n denotes the number of molecular and its influence on film drainage and stability.48 In turn, foams
diameters. and emulsions could be obtained without a stabilizing agent
(Figure S5 in Supporting Information), opening new
perspectives in fields such as cosmetics or material design.

■
bond length differences, the radius of gyration Rg of the
copolymer may be estimated using the following scaling law.42
ASSOCIATED CONTENT
⎛N l ⎞ 3/5
* Supporting Information
S
R g ≈ ⎜ tot s ⎟ D, The Supporting Information is available free of charge on the
⎝ Ns D ⎠ (2) ACS Publications website at DOI: 10.1021/acsmacro-
with Ntot = Nb + Ns the total number of monomers in the comb lett.5b00535.
and D the diameter of the comb. In our case, Ntot ≈ 460, Nb = Details on the phase diagram of the bulk copolymer melt
13 (including the alkyl linker), and D = 2lsc ≈ 9 nm. Calculation using Differential Scanning Calorimetry, the rheology of
gives Rg ≈ 24 nm, a value of the same order of magnitude than the melt, its surface tension, close-ups on the stratified
lc. Thus, lc is likely related to the radius of gyration of DBP-732. regions at the top of a vertical thin film of DBP-732 and
We note that the geometrical features of DBP-732 molecules pictures of foams generated with DBP-732 (PDF).
indicate that they must have a non-negligible persistence length Illustrates the drainage process of a vertical film of DBP-
and should therefore be prolate rods rather than spheres. 732 (AVI).

■
We therefore propose the following hypothesis (Figure 4b)
to explain our observations: while the bulk polymer does not AUTHOR INFORMATION
show any ordering transition (as can be seen in Figure S1 in the Corresponding Author
Supporting Information), the presence of the interfaces and the *E-mail: [email protected]..
induced confinement lead to a stratified organization the
characteristic length of which is the radius of gyration of the Present Addresses
‡
individual molecules. As the surface tension of DBP-732 γ = CNRS, ICMCB, UPR9048, F-33600 Pessac, France.
§
20.7 ± 0.2 mN·m−1 (Figure S4 in Supporting Information) is Laboratoire Matière et Systèmes Complexes, CNRS UMR
close to that of pure PDMS of similar chain length,46 γPDMS = 7057 and Université Paris Diderot, 10 rue Alice Domon et
20.1 ± 0.2 mN·m−1, the first layer at the interface is probably Léonie Duquet, 75013 Paris, France.
composed of molecules that orient their PDMS backbone to Notes
the surrounding air.47 Such a molecular conformation may help The authors declare no competing financial interest.
impose a preferential order of the rod-like copolymers close to
the interface, thus, encouraging stratification. This mechanism
may also explain the observation of stratification in films several
■ ACKNOWLEDGMENTS
This project was funded by an ERC Starting Grant (Agreement
hundred nm thick. Once the film thickness is of the order of a 307280-POMCAPS). We received additional financial support
few times the radius of gyration, the isotropic bulk liquid gives from TECLIS and BPI France. This work has benefited from
way to a layered system. How exactly the polymers organize in the support of the “Investissements d’Avenir” of the LabEx
these layers remains an open question and will be the subject of PALM (ANR-10-LABX-0039-PALM). We thank J. Venzmer,
future investigations. M. Zeghal, C. Gay, E. Rio, L. Champougny, B. Scheid, D.
1147 DOI: 10.1021/acsmacrolett.5b00535
ACS Macro Lett. 2015, 4, 1144−1148
ACS Macro Letters Letter

Langevin, L. Léger, H. Plantefève, F. Restagno, P. Guénoun, R. (38) Langevin, D.; Marquez-Beltran, C.; Delacotte, J. Adv. Colloid
von Klitzing, P.-A. Albouy, and A. Cagna for fruitful discussions. Interface Sci. 2011, 168 (1−2), 124−134.

■
(39) Stubenrauch, C.; von Klitzing, R. J. Phys.: Condens. Matter 2003,
REFERENCES 15, R1197−R1232.
(40) Green, P. F. J. Polym. Sci., Part B: Polym. Phys. 2003, 41 (19),
(1) Craster, R.; Matar, O. Rev. Mod. Phys. 2009, 81 (3), 1131−1198. 2219−2235.
(2) Israelachvili, J. N. Intermolecular and Surface Forces, 3rd ed.; (41) Tverdokhlebova, I. I. Russ. Chem. Rev. 1977, 46 (7), 657−670.
Academic Press: New York, 2011. (42) Birshtein, T. M.; Borisov, O. V.; Zhulina, Y. B.; Khokhlov, A. R.;
(3) Pindak, R.; Moncton, D. E.; Davey, S. C.; Goodby, J. W. Phys. Yurasova, T. A. Polym. Sci. U.S.S.R. 1987, 29 (6), 1293−1300.
Rev. Lett. 1981, 46 (17), 1135−1138. (43) Ding, Y.; Kisliuk, A.; Sokolov, A. P. Macromolecules 2004, 37
(4) Pikina, E. S.; Ostrovskii, B. I.; de Jeu, W. H. Eur. Phys. J. E: Soft (1), 161−166.
Matter Biol. Phys. 2015, 38 (3), 13. (44) Mark, J. E.; Curro, J. G. J. Chem. Phys. 1983, 79 (11), 5705.
(5) Picano, F.; Oswald, P.; Kats, E. Phys. Rev. E: Stat. Phys., Plasmas, (45) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
Fluids, Relat. Interdiscip. Top. 2001, 63 (2), 1−9. A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, No. 12, S1−S19.
(6) Sonin, A. A.; Langevin, D. Eur. Lett. 1993, 22 (4), 271−277. (46) Polymer Data Handbook; Mark, J. E., Ed.; Oxford University
(7) Bergeron, V.; Radke, C. J. Langmuir 1992, 8 (12), 3020−3026. Press: New York, 1999.
(8) Saint-Jalmes, A.; Sonin, A. A.; Delsanti, M.; Guenoun, P.; Yang, J.; (47) Sauer, B. B.; Dee, G. T. J. Colloid Interface Sci. 1994, 162 (1),
Mays, J. W.; Langevin, D. Langmuir 2002, 18 (6), 2103−2110. 25−35.
(9) Kleinschmidt, F.; Stubenrauch, C.; Delacotte, J.; von Klitzing, R.; (48) Champougny, L.; Scheid, B.; Restagno, F.; Vermant, J.; Rio, E.
Langevin, D. J. Phys. Chem. B 2009, 113 (12), 3972−3980. Soft Matter 2015, 11, 2758.

■
(10) Von Klitzing, R.; Thormann, E.; Nylander, T.; Langevin, D.;
Stubenrauch, C. Adv. Colloid Interface Sci. 2010, 155 (1−2), 19−31. NOTE ADDED AFTER ASAP PUBLICATION
(11) Alcoutlabi, M.; McKenna, G. B. J. Phys.: Condens. Matter 2005,
17 (15), R461−R524. This paper was published ASAP on October 2, 2015, with an
(12) Kim, S.; Roth, C. B.; Torkelson, J. M. J. Polym. Sci., Part B: error in the abstract graphic. The corrected version was
Polym. Phys. 2008, 46 (24), 2754−2764. reposted on October 7, 2015.
(13) Reiter, G. Phys. Rev. Lett. 1992, 68 (1), 75−78.
(14) Seemann, R.; Herminghaus, S.; Jacobs, K. Phys. Rev. Lett. 2001,
86 (24), 5534−5537.
(15) Kargupta, K.; Sharma, A. Phys. Rev. Lett. 2001, 86 (20), 4536−
4539.
(16) Collin, B.; Chatenay, D.; Coulon, G.; Ausserre, D.; Gallot, Y.
Macromolecules 1992, 25 (5), 1621−1622.
(17) Huang, E.; Rockford, L.; Russell, T. P.; Hawker, C. J. Nature
1998, 395 (6704), 757−758.
(18) Fasolka, M. J.; Mayes, A. M. Annu. Rev. Mater. Res. 2001, 31 (1),
323−355.
(19) Mann, E. K.; Langevin, D. Langmuir 1991, 7, 1112−1117.
(20) Mann, E. K.; Hénon, S.; Langevin, D.; Meunier, J. J. Phys. II
1992, 2 (9), 1683−1704.
(21) Bodiguel, H.; Frétigny, C. Phys. Rev. Lett. 2006, 97 (26), 266105.
(22) Bodiguel, H.; Fretigny, C. Eur. Phys. J. E: Soft Matter Biol. Phys.
2006, 19 (2), 185−193.
(23) Bodiguel, H.; Fretigny, C. Macromolecules 2007, 40 (20), 7291−
7298.
(24) Forrest, J. A.; Dalnoki-Veress, K.; Stevens, J. R.; Dutcher, J. R.
Phys. Rev. Lett. 1996, 77 (10), 2002−2005.
(25) Forrest, J. A.; Dalnoki-Veress, K.; Dutcher, J. R. Phys. Rev. E:
Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1997, 56 (5), 5705−
5716.
(26) Radzilowski, L. H.; Carvalho, B. L.; Thomas, E. L. J. Polym. Sci.,
Part B: Polym. Phys. 1996, 34 (17), 3081−3093.
(27) Croll, A. B.; Dalnoki-Veress, K. Soft Matter 2010, 6 (21), 5547−
5553.
(28) Mysels, K. J.; Frankel, S.; Shinoda, K. Soap Films: Studies of Their
Thinning and a Bibliography; Pergamon Press: Elmsford, NY, 1959.
(29) Sheludko, A. Adv. Colloid Interface Sci. 1967, 1, 391−464.
(30) Bergeron, V. J. Phys.: Condens. Matter 1999, 11, R215−R238.
(31) Nierstrasz, V.; Frens, G. J. Colloid Interface Sci. 1999, 215 (1),
28−35.
(32) Adami, N.; Dorbolo, S.; Caps, H. Phys. Rev. E 2011, 84 (4), 1−8.
(33) Schwartz, L.; Roy, R. J. Colloid Interface Sci. 1999, 218 (1), 309−
323.
(34) Braun, R. J.; Snow, S. A.; Naire, S. 2002, 281−314.
(35) Barigou, M.; Davidson, J. F. Chem. Eng. Sci. 1994, 49 (11),
1807−1819.
(36) Debrégeas, G.; De Gennes, P.-G.; Brochard-Wyart, F. Science
1998, 279 (5357), 1704−1707.
(37) Claesson, P. M.; Ederth, T.; Bergeron, V. Adv. Colloid Interface
Sci. 1996, 67, 119−183.

1148 DOI: 10.1021/acsmacrolett.5b00535

ACS Macro Lett. 2015, 4, 1144−1148