We investigate the local viscosity of a polymer glass around its glass transition temperature by using environment-sensitive fluorescent molecular rotors embedded in the polymer matrix. The fluorescence of the rotors depends on the local viscosity, and measuring the fluorescence intensity and lifetime of the probe therefore allows us to measure the local free volume in the polymer glass when going through the glass transition. This also allows us to study the local viscosity and free volume when the polymer film is put under an external stress. We find that the film does not flow homogeneously but undergoes shear banding that is visible as a spatially varying free volume and viscosity.

1.
S.-W.
Kuo
,
H.-C.
Kao
, and
F.-C.
Chang
, “
Thermal behavior and specific interaction in high glass transition temperature PMMA copolymer
,”
Polymer
44
(
22
),
6873
6882
(
2003
).
2.
S.
Alford
and
M.
Dole
, “
Specific heat of synthetic high polymers. VI. A study of the glass transition in polyvinyl chloride
,”
J. Am. Chem. Soc.
77
(
18
),
4774
4777
(
1955
).
3.
A.
Rudin
and
D.
Burgin
, “
Effects of molecular weight and chain ends on glass transition of polystyrene
,”
Polymer
16
(
4
),
291
297
(
1975
).
4.
P.
Pan
,
B.
Zhu
,
T.
Dong
,
K.
Yazawa
,
T.
Shimizu
,
M.
Tansho
, and
Y.
Inoue
, “
Conformational and microstructural characteristics of poly(l-lactide) during glass transition and physical aging
,”
J. Chem. Phys.
129
(
18
),
184902
(
2008
).
5.
D.
Cangialosi
, “
Dynamics and thermodynamics of polymer glasses
,”
J. Phys.: Condens. Matter
26
(
15
),
153101
(
2014
).
6.
E.
Vidal Russell
and
N. E.
Israeloff
, “
Direct observation of molecular cooperativity near the glass transition
,”
Nature
408
(
6813
),
695
698
(
2000
).
7.
C.
Balbuena
,
M.
Mariel Gianetti
, and
E.
Rodolfo Soulé
, “
A structural study and its relation to dynamic heterogeneity in a polymer glass former
,”
Soft Matter
17
(
12
),
3503
3512
(
2021
).
8.
R. A.
Riggleman
,
H.-N.
Lee
,
M. D.
Ediger
, and
J. J.
de Pablo
, “
Heterogeneous dynamics during deformation of a polymer glass
,”
Soft Matter
6
(
2
),
287
291
(
2010
).
9.
K.
Yoshimoto
,
T. S.
Jain
,
K.
Van Workum
,
P. F.
Nealey
, and
J. J.
de Pablo
, “
Mechanical heterogeneities in model polymer glasses at small length scales
,”
Phys. Rev. Lett.
93
(
17
),
175501
(
2004
).
10.
J. R.
Siekierzycka
,
C.
Hippius
,
F.
Würthner
,
R. M.
Williams
, and
A. M.
Brouwer
, “
Polymer glass transitions switch electron transfer in individual molecules
,”
J. Am. Chem. Soc.
132
(
4
),
1240
1242
(
2010
).
11.
C. J.
Ellison
,
S. D.
Kim
,
D. B.
Hall
, and
J. M.
Torkelson
, “
Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements
,”
Eur. Phys. J. E
8
(
2
),
155
166
(
2002
).
12.
K. A.
Willets
,
O.
Ostroverkhova
,
M.
He
,
R. J.
Twieg
, and
W. E.
Moerner
, “
Novel fluorophores for single-molecule imaging
,”
J. Am. Chem. Soc.
125
(
5
),
1174
1175
(
2003
).
13.
H.-N.
Lee
,
K.
Paeng
,
S. F.
Swallen
, and
M. D.
Ediger
, “
Dye reorientation as a probe of stress-induced mobility in polymer glasses
,”
J. Chem. Phys.
128
(
13
),
134902
(
2008
).
14.
H.-N.
Lee
,
K.
Paeng
,
S. F.
Swallen
,
M. D.
Ediger
,
R. A.
Stamm
,
G. A.
Medvedev
, and
J. M.
Caruthers
, “
Molecular mobility of poly(methyl methacrylate) glass during uniaxial tensile creep deformation
,”
J. Polym. Sci., Part B: Polym. Phys.
47
(
17
),
1713
1727
(
2009
).
15.
H.-N.
Lee
,
K.
Paeng
,
S. F.
Swallen
, and
M. D.
Ediger
, “
Direct measurement of molecular mobility in actively deformed polymer glasses
,”
Science
323
(
5911
),
231
234
(
2009
).
16.
H.-N.
Lee
and
M. D.
Ediger
, “
Interaction between physical aging, deformation, and segmental mobility in poly(methyl methacrylate) glasses
,”
J. Chem. Phys.
133
(
1
),
014901
(
2010
).
17.
K.
Hebert
and
M. D.
Ediger
, “
Reversing strain deformation probes mechanisms for enhanced segmental mobility of polymer glasses
,”
Macromolecules
50
(
3
),
1016
1026
(
2017
).
18.
B.
Bending
and
M. D.
Ediger
, “
Comparison of mechanical and molecular measures of mobility during constant strain rate deformation of a PMMA glass
,”
J. Polym. Sci., Part B: Polym. Phys.
54
(
19
),
1957
1967
(
2016
).
19.
H.-N.
Lee
,
R. A.
Riggleman
,
J. J.
de Pablo
, and
M. D.
Ediger
, “
Deformation-induced mobility in polymer glasses during multistep creep experiments and simulations
,”
Macromolecules
42
(
12
),
4328
4336
(
2009
).
20.
R. A.
Riggleman
,
H.-N.
Lee
,
M. D.
Ediger
, and
J. J.
de Pablo
, “
Free volume and finite-size effects in a polymer glass under stress
,”
Phys. Rev. Lett.
99
(
21
),
215501
(
2007
).
21.
D. B.
Hall
,
A.
Dhinojwala
, and
J. M.
Torkelson
, “
Translation-rotation paradox for diffusion in glass-forming polymers: The role of the temperature dependence of the relaxation time distribution
,”
Phys. Rev. Lett.
79
(
1
),
103
106
(
1997
).
22.
H.-N.
Lee
and
M. D.
Ediger
, “
Mechanical rejuvenation in poly(methyl methacrylate) glasses? Molecular mobility after deformation
,”
Macromolecules
43
(
13
),
5863
5873
(
2010
).
23.
J.-B.
Salmon
,
A.
Colin
,
S.
Manneville
, and
F.
Molino
, “
Velocity profiles in shear-banding wormlike micelles
,”
Phys. Rev. Lett.
90
(
22
),
228303
(
2003
).
24.
O.
Radulescu
,
P. D.
Olmsted
,
J. P.
Decruppe
,
S.
Lerouge
,
J.-F.
Berret
, and
G.
Porte
, “
Time scales in shear banding of wormlike micelles
,”
Europhys. Lett.
62
(
2
),
230
(
2003
).
25.
F.
Varnik
,
L.
Bocquet
, and
J.-L.
Barrat
, “
A study of the static yield stress in a binary Lennard-Jones glass
,”
J. Chem. Phys.
120
(
6
),
2788
2801
(
2004
).
26.
P.
Tapadia
,
S.
Ravindranath
, and
S.-Q.
Wang
, “
Banding in entangled polymer fluids under oscillatory shearing
,”
Phys. Rev. Lett.
96
(
19
),
196001
(
2006
).
27.
J.
Cao
and
A. E.
Likhtman
, “
Shear banding in molecular dynamics of polymer melts
,”
Phys. Rev. Lett.
108
(
2
),
028302
(
2012
).
28.
A.
Wisitsorasak
and
P. G.
Wolynes
, “
Dynamical theory of shear bands in structural glasses
,”
Proc. Natl. Acad. Sci.
114
(
6
),
1287
1292
(
2017
).
29.
S.
Ravindranath
,
S.-Q.
Wang
,
M.
Olechnowicz
, and
R. P.
Quirk
, “
Banding in simple steady shear of entangled polymer solutions
,”
Macromolecules
41
(
7
),
2663
2670
(
2008
).
30.
R. O.
Loutfy
and
D. M.
Teegarden
, “
Effect of polymer chain tacticity on the fluorescence of molecular rotors
,”
Macromolecules
16
(
3
),
452
456
(
1983
).
31.
K. Y.
Law
and
R. O.
Loutfy
, “
Fluorescence probe for microenvironments: On the fluorescence properties of p-N,N-dialkylaminobenzylidenemalononitrile in polymer matrices
,”
Polymer
24
(
4
),
439
442
(
1983
).
32.
R. O.
Loutfy
, “
High-conversion polymerization of fluorescence probes. 1. Polymerization of methyl methacrylate
,”
Macromolecules
14
(
2
),
270
275
(
1981
).
33.
R. D.
Priestley
,
M. K.
Mundra
,
N. J.
Barnett
,
L. J.
Broadbelt
, and
J. M.
Torkelson
, “
Effects of nanoscale confinement and interfaces on the glass transition temperatures of a series of poly(n-methacrylate) films
,”
Aust. J. Chem.
60
(
10
),
765
771
(
2007
).
34.
S.
Kim
,
C. B.
Roth
, and
J. M.
Torkelson
, “
Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: Novel, self-referencing fluorescence method
,”
J. Polym. Sci., Part B: Polym. Phys.
46
(
24
),
2754
2764
(
2008
).
35.
S.
Kim
,
S. A.
Hewlett
,
C. B.
Roth
, and
J. M.
Torkelson
, “
Confinement effects on glass transition temperature, transition breadth, and expansivity: Comparison of ellipsometry and fluorescence measurements on polystyrene films
,”
Eur. Phys. J. E
30
(
1
),
83
(
2009
).
36.
R. O.
Loutfy
and
B. A.
Arnold
, “
Effect of viscosity and temperature on torsional relaxation of molecular rotors
,”
J. Phys. Chem.
86
(
21
),
4205
4211
(
1982
).
37.
K. Y.
Law
and
R. O.
Loutfy
, “
Spectroscopy of dyes in polymer matrixes: Dual fluorescence of p-[(dialkylamino)benzylidene]malononitrile
,”
Macromolecules
14
(
3
),
587
591
(
1981
).
38.
J. C.
Hooker
and
J. M.
Torkelson
, “
Coupling of probe reorientation dynamics and rotor motions to polymer relaxation as sensed by second harmonic generation and fluorescence
,”
Macromolecules
28
(
23
),
7683
7692
(
1995
).
39.
J. S.
Royal
and
J. M.
Torkelson
, “
Monitoring the molecular scale effects of physical aging in polymer glasses with fluorescence probes
,”
Macromolecules
23
(
14
),
3536
3538
(
1990
).
40.
J. S.
Royal
and
J. M.
Torkelson
, “
Molecular-scale asymmetry and memory behavior in poly(vinyl acetate) monitored with mobility-sensitive fluorescent molecules
,”
Macromolecules
25
(
6
),
1705
1710
(
1992
).
41.
J. S.
Royal
and
J. M.
Torkelson
, “
Physical aging effects on molecular-scale polymer relaxations monitored with mobility-sensitive fluorescent molecules
,”
Macromolecules
26
(
20
),
5331
5335
(
1993
).
42.
T.
Suhina
,
D.
Bonn
,
B.
Weber
, and
A. M.
Brouwer
, “
Photophysics of fluorescent contact sensors based on the dicyanodihydrofuran motif
,”
Chemphyschem
22
(
2
),
221
227
(
2021
).
43.
B.
Weber
,
T.
Suhina
,
T.
Junge
,
L.
Pastewka
,
A. M.
Brouwer
, and
D.
Bonn
, “
Molecular probes reveal deviations from Amontons’ law in multi-asperity frictional contacts
,”
Nat. Commun.
9
(
1
),
888
(
2018
).
44.
S. J.
Lord
,
N. R.
Conley
,
H.-l. D.
Lee
,
S. Y.
Nishimura
,
A. K.
Pomerantz
,
K. A.
Willets
,
Z.
Lu
,
H.
Wang
,
N.
Liu
,
R.
Samuel
,
R.
Weber
,
A.
Semyonov
,
M.
He
,
R. J.
Twieg
, and
W. E.
Moerner
, “
DCDHF fluorophores for single-molecule imaging in cells
,”
Chemphyschem
10
(
1
),
55
65
(
2009
).
45.
A.-Y.
Jee
,
E.
Bae
, and
M.
Lee
, “
Internal motion of an electronically excited molecule in viscoelastic media
,”
J. Chem. Phys.
133
(
1
),
014507
(
2010
).
46.
A.-Y.
Jee
,
H.
Lee
,
Y.
Lee
, and
M.
Lee
, “
Determination of the elastic modulus of poly(ethylene oxide) using a photoisomerizing dye
,”
Chem. Phys.
422
,
246
250
(
2013
).
47.
S.
Saito
, “
Temperature dependence of dielectric relaxation behavior for various polymer systems
,”
Kolloid-Z. Z. Polym.
189
(
2
),
116
125
(
1963
).
48.
A.
Zaccone
and
E. M.
Terentjev
, “
Disorder-assisted melting and the glass transition in amorphous solids
,”
Phys. Rev. Lett.
110
(
17
),
178002
(
2013
).
49.
R. B.
Bogoslovov
,
C. M.
Roland
,
A. R.
Ellis
,
A. M.
Randall
, and
C. G.
Robertson
, “
Effect of silica nanoparticles on the local segmental dynamics in poly(vinyl acetate)
,”
Macromolecules
41
(
4
),
1289
1296
(
2008
).
50.
D.
Anwand
,
F. W.
Müller
,
B.
Strehmel
, and
K.
Schiller
, “
Determination of the molecular mobility and the free volume of thin polymeric films with fluorescence probes
,”
Makromol. Chem.
192
(
9
),
1981
1991
(
1991
).
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