Abstract
By performing Atomic Force Microscopy measurements of pull-off force as a function of the temperature, we were able to probe the dynamic of supported thin polystyrene (PS) films. Thermal transitions induce modifications in the surface energy, roughness and surface modulus that are clearly detected by AFM and related to PS chain relaxation mechanisms. We demonstrated the existence of three transition temperatures that can be associated to the relaxation of polymer chains located at different depth regions within the polymer film. Independently of the film thickness, we have confirmed the presence of a region of high mobility for the polymer chains at the free interface. The thickness of this region is estimated to be above 7nm. The detection of a transition only present for film thicker than the gyration radius Rg is linked to the dynamics of polymer chains in a bulk conformation (i.e. not in contact with the free interface). We claim here that our results demonstrate, in agreement with other techniques, the stratification of thin polymer film depth profile in terms of relaxation behavior.
Graphical abstract
Similar content being viewed by others
References
D. Siniscalco et al., J. Phys. Chem. C 117, 7391 (2013).
T. Kerle et al., Macromolecules 34, 3484 (2001).
H.-C. Scheer et al., J. Vac. Sci. Technol. B 25, 2392 (2007).
A. Bansal et al., Nat. Mater. 4, 693 (2005).
S. Napolitano, D. Cangialosi, Macromolecules 46, 8051 (2013).
G. Reiter, S. Napolitano, J. Polym. Sci. B 48, 2544 (2010).
G. Reiter, Europhys. Lett. 23, 579 (1993).
J.L. Keddie, R.A.L. Jones, R.A. Cory, Europhys. Lett. 27, 59 (1994).
C.B. Roth, J.R. Dutcher, in Soft Materials: Structure and Dynamics, edited by John R. Dutcher, Alejandro G. Marangoni, (Marcel Dekker, New York, 2005) pp. 1-38.
G. Vignaud et al., Langmuir 21, 8601 (2005).
P.G. de Gennes, Eur. Phys. J. E 2, 201 (2000).
Y. Grohens et al., Eur. Phys. J. E 8, 217 (2002).
C.J. Ellison, J.M. Torkelson, Nat. Mater. 2, 695 (2003).
K. Tanaka et al., J. Phys. Chem. B 113, 4571 (2009).
J.A. Forrest, J. Mattsson, Phys. Rev. E 61, R53 (2000).
Z. Ao, S. Li, Nanosci. Res. Lett. 6, 243 (2011).
T. Miyazaki, K. Nishida, T. Kanaya, Phys. Rev. E 69, 061803 (2004).
D. Long, F. Lequeux, Eur. Phys. J. E 4, 371 (2001).
S. Herminghaus, Eur. Phys. J. E 8, 237 (2002).
M. Benzaquen, T. Salez, E. Raphaël, Eur. Phys. J. E 36, 1 (2013).
A. Dequidt et al., Eur. Phys. J. E 35, 1 (2012).
V.M. Boucher et al., Thermochim. Acta 575, 233 (2014).
B. Zuo et al., Soft Matter 9, 9376 (2013).
M.Y. Efremov et al., Phys. Rev. E 86, 021501 (2012).
O. Bäumchen et al., Phys. Rev. Lett. 109, 055701 (2012).
D. Hudzinskyy et al., Macromolecules 44, 2299 (2011).
P. Bernazzani, R. Sanchez, J. Thermal Anal. Calorim. 96, 727 (2009).
S. Gao, Y.P. Koh, S.L. Simon, Macromolecules 46, 562 (2013).
A. El Ouakili et al., Thin Solid Films 519, 2031 (2011).
F. Dinelli et al., Macromolecules 44, 987 (2011).
M. Hinz et al., Eur. Polym. J. 40, 957 (2004).
K. Miyake, N. Satomi, S. Sasaki, Appl. Phys. Lett. 89, 031925 (2006).
D. Silbernagl, H. Sturm, B. Cappella, Langmuir 25, 5091 (2009).
S.K. Kaliappan, B. Cappella, Polymer 46, 11416 (2005).
B. Cappella, D. Silbernagl, Thin Solid Films 516, 1952 (2008).
T. Kajiyama, K. Tanaka, A. Takahara, Macromolecules 30, 280 (1997).
S. Sills et al., J. Appl. Phys. 98, 014302 (2005).
S. Sills et al., J. Chem. Phys. 120, 5334 (2004).
O.K.C. Tsui et al., Macromolecules 41, 1465 (2008).
S. Ge et al., Phys. Rev. Lett. 85, 2340 (2000).
J. Fu, B. Li, Y. Han, J. Chem. Phys. 123, 064713 (2005).
D.B. Knorr et al., J. Chem. Phys. 134, 104502 (2011).
F. Dinelli, C. Buenviaje, R.M. Overney, J. Chem. Phys. 113, 2043 (2000).
O.K.C. Tsui et al., Macromolecules 33, 4198 (2000).
V.N. Bliznyuk, H.E. Assender, G.A.D. Briggs, Macromolecules 35, 6613 (2002).
Z. Yang et al., Science 38, 1676 (2010).
J.H. Teichroeb, J.A. Forrest, Phys. Rev. Lett. 91, 016104 (2003).
M. Daoud et al., Macromolecules 8, 804 (1975).
G. Lecollinet et al., Langmuir 25, 7828 (2009).
M. Mukherjee et al., Polymer 54, 4669 (2013).
R. Levy, M. Maaloum, Nanotechnology 13, 33 (2002).
L. Chen et al., Appl. Phys. Lett. 93, 053503 (2008).
H.-J. Butt, B. Capella, M. Kappl, Surf. Sci. Rep. 59, 1 (2005).
Y. Sun, B. Akhremitchev, G.C. Walker, Langmuir 20, 5837 (2004).
H.-J. Butt et al., Soft Matter 6, 5930 (2010).
I. Sridhar, K.L. Johnson, N.A. Fleck, J. Phys. D: Appl. Phys. 30, 1710 (1997).
G. Castellanos, E. Arzt, M. Kamperman, Langmuir 27, 7752 (2011).
N. Lakhera et al., Int. J. Adhesion Adhesives 44, 184 (2013).
Y. Ando, Langmuir 24, 1418 (2007).
H. Kim, B. Smit, J. Jang, J. Phys. Chem. C 116, 21923 (2012).
N.W. Moore, Langmuir 27, 3678 (2011).
R. Jones et al., Langmuir 18, 8045 (2002).
R. Long, C.-Y. Hui, Proc. Royal Soc. A 465, 961 (2009).
J. Drelich, Z. Xu, J. Masliyah, Langmuir 22, 8850 (2006).
S. Yang et al., Langmuir 24, 743 (2008).
J. Jang, J. Sung, G.C. Schatz, J. Phys. Chem. C 111, 4648 (2007).
H. Awada et al., Thin Solid Films 519, 3690 (2011).
S. Wu, J. Phys. Chem. 74, 632 (1970).
O. Marti, in Modern Tribology Handbook, edited by B. Bushnan (CRC Press, New York, 2001). .
K.R. Shull, Mater. Sci. Engin. R 36, 1 (2002).
G. Luengo et al., Langmuir 14, 3873 (1998).
A.D. Schwab et al., Macromolecules 33, 4903 (2000).
S.E. Keinath, R.F. Boyer, J. Appl. Polym. Sci. 26, 2077 (1981).
L. Gong, X. Zhang, Y. Shi, Eur. Polym. J. 47, 1931 (2011).
D. Silbernagl, B. Cappella, Scanning 32, 282 (2010).
P.C. Chung, E. Glynos, P.F. Green, Langmuir 30, 15200 (2014).
O.K.C. Tsui, in Polymer Thin Films, edited by Ophelia K.C. Tsui, Thomas P. Russell (World Scientific, Singapore, 2008) pp. 267-294.
L. Singh, P.J. Ludovice, C.L. Henderson, Thin Solid Films 449, 231 (2004).
Y. Fujii et al., Macromolecules 42, 7418 (2009).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Delorme, N., Chebil, M.S., Vignaud, G. et al. Experimental evidence of ultrathin polymer film stratification by AFM force spectroscopy. Eur. Phys. J. E 38, 56 (2015). https://doi.org/10.1140/epje/i2015-15056-9
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1140/epje/i2015-15056-9