RESEARCH NEWS
Ultra-Low Surface Energy Polymers:
The Molecular Design Requirements
John Tsibouklis* and Thomas G. Nevell
In this Research News contribution, the molecular design requirements for the syn-
thesis of polymeric materials that can be used for the fabrication of readily accessi-
ble film structures with ultra-low surface energy characteristics are described.
1. Introduction
Low surface energy finishes are important in many practical
applications. Although poly(tetrafluoroethylene), PTFE, may
be regarded as the benchmark low surface energy material,
this polymer has limitations due to its low oil repellency and
to its microcrystalline surface structure. Considerable re-
search efforts, therefore, are directed towards the develop-
ment of alternative, non-wettable, low surface energy poly-
meric materials with good film-forming characteristics. The
impetus for those activities is provided by commercial appli-
cations in aerospace, lithography, clothing, and integrated sen-
sors, and by the need for environmentally friendly protection
against biological and other fouling.[1±9]
In general, non-stick materials are characterized by low
surface energies (c, experimentally resolvable into non-polar
(Lifshitz±van der Waals) cLW, Lewis acid c+, and Lewis base
c± contributions).[10,11] For polymeric materials, the value of
c [mJ m±2] is determined mainly by the chemical structure at
the surface: values for some constituent groups decrease in
the order >CH2 (36) > -CH3 (30) > >CF2 (23) > -CF3 (15).[12±16]
Amorphous materials exhibit lower surface energy values
than crystalline counterparts.[17]
2. Surface Energy Determinations
Measurements of advancing and receding liquid±solid con-
tact angles h of polar, non-polar, and hydrogen (H)-bonding
solvents may be used to investigate surface roughness and het-
erogeneity and, with surface-tension component theory, to
evaluate surface energy contributions.[10,11] According to this
approach, which is perhaps the most powerful for the evalua-
± ing characteristics, and surface energies of several classes of
[*] Dr. J. Tsibouklis, Dr. T. G. Nevell
School of Pharmacy and Biomedical Sciences, University of Portsmouth
St. Michael's Building, White Swan Road, Portsmouth PO1 2DT (UK)
E-mail: john.tsibouklis@port.ac.uk
Adv. Mater. 2003, 15, No. 7±8, April 17 DOI: 10.1002/adma.200301638
H2C CR C
O
O (CH2)2 (CF2)n CF3
H3C Si (CH2)3 O (CH2)2 (CF2)n CF3
tion of surface energy, the surface energy (solid, cS; liquid, cL)
combines the three contributions according to:
cS = cSLW + 2(c+S + cS±)1/2 (1a)
cL = cLLW + 2(c+L + cL±)1/2 (1b)
Values of cSLW, cS+, and cS± can be calculated (from Eq. 2)
from measurements of h for three characterized liquids; typi-
cally water, diiodomethane, and ethylene glycol.
cL (1 + cos h) = 2[(cSLW cLLW)1/2 + (cS+ cL±)1/2 + (cS± cL+)1/2] (2)
In view of the uncertainties associated with the use of hy-
drocarbon liquids for the evaluation of the surface free ener-
gies of perfluorocarbon solids,[18] the surface energy of PTFE,
Teflon, is normally determined for comparison.
The usefulness of the surface-tension-component approach
stems from the fact that it is capable of unmasking the effects
of the individual contributors to the total energy of a surface.
This is exemplified in a study of the time-dependence of the
surface energy of poly(1H,1H,2H,2H-perfluorodecanoyl diita-
conate), Figure 1.[19] Thus, for films of this polymer, although
cS appears to show little time dependence, the data show that
the Lewis base component c± increases with time. This obser-
vation is of some importance with respect to the potential util-
ity of the material in some applications.
3. The Molecular Design Requirements
It has been suggested that amorphous, comb-like polymers
possessing a flexible linear backbone onto which side chains
with low intermolecular interactions are attached will exhibit
low values of cS.[20] The synthesis, characterization, film form-
readily accessible materials that may comply with these
molecular design requirements have been described
(Scheme 1).[21±25]
Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 647

RESEARCH NEWS
8
Total surface energy
Energy / mJ m-2
6
van der Waals contribution
4 and backbone flexibility. Typically, the more flexible fluorosi-
Lewis-base contribution
2
0
Lewis-acid contribution
0 1000 2000 3000
Time / s
Fig. 1. Time dependence of surface energy contributions for
poly(1H,1H,2H,2H-perfluorodecanoyl diitaconate) film structures at 25.0 C as
calculated from recently advanced contact angles of drops of water, diiodo-
methane, and ethylene glycol under saturated vapor. The stepwise increase in
cS± reflects changes in surface structure induced by interaction with -OH
(water, ethylene glycol) [19].
Consideration of the surface energy components associated
with each member of the homologous series of materials pre-
sented in Table 1 reveals that, in addition to surface roughness
(the effects of which can be assessed by combining advanced
contact angle measurements with receding contact angle de-
terminations), the wetting behavior is determined by four
structural features of the macromolecule, namely: i) nature of
the pendent chain; ii) length of the pendent chain; iii) nature
of the linking moiety; and iv) nature of the polymer back-
bone.
The data show that the nature of the pendent chain has a
most profound effect in determining the surface energy of the
material, with all fluoro-substituted compounds exhibiting
surface energies that are markedly lower than those of corre-
sponding alkyl-substituted macromolecules (20±35 mJ m±2).
The influence of the length of the pendent fluorocarbon or
hydrocarbon moiety is also evident: general trends of lower
surface energy with increasing chain length are observed.
However, as the length of the pendent chain increases, the
average surface roughness of the corresponding film struc-
tures follows a similar trend. Nonetheless, the incorporation
of a long perfluorocarbon side chain is an essential element of
the molecular design for such materials, as it serves to inhibit
the absorption of liquids by the bulk sample; only the materi-
als with longer side chains, and rougher surfaces, (PFA9,
PFA7, PFMA9, PFMA7, and PFE9), have been found to be
resistant to penetration by water or organic liquids.[21±25]
O O
H2C CR C O (CH2)2 (CF2)n CF3 H3C Si
Scheme 1. Typical low surface energy polymers. Poly(perfluoroalkylacrylate)s [17]: (R = H): n = 3,
PFA3; n = 5, PFA5; n = 7, PFA7; n = 9, PFA9. Poly(methylpropenoxyperfluoroalkylsiloxane)s [20,21]:
n = 3, PFE3; n = 5, PFE5; n = 7, PFE7; n = 9, PFE9. Poly(perfluoroalkylmethacrylate)s [19]: (R = CH3):
n = 3, PFMA3; n = 5, PFMA5; n = 7, PFMA7; n = 9, PFMA9. Poly(perfluoroalkyldiitaconate)s [18]:
(R = CH2COOR¢; R¢ = (CH2)2(CF2)nCF3): n = 3, PFI3; n = 5, PFI5; n = 7, PFI7; n = 9, PFI9.
648 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Tsibouklis, T. G. Nevell/Ultra-Low Surface Energy Polymers
Comparison of the total surface energy values characteriz-
ing each of the homologous series of macromolecules consid-
ered (cS, Table 1) highlights the relative significance of the
two main molecular design requirements for the construction
of low surface energy polymers, namely fluoro-substitution
loxanes exhibit higher surface energy values (ca. 12±17 mJ m±2
for n = 3±9) than their acrylate counterparts (ca. 6±13 mJ m±2
for n = 3±9). This behavior may be rationalized at the submo-
lecular level in terms of two possible phenomena, namely:
i) thermal crosslinking, which makes the polysiloxane back-
4000
bone more rigid than that of polyacrylates (note that ther-
mally crosslinked PFE9 exhibits a value of cS which is ca.
3 mJ m±2 greater than that of a parallel sample which was not
subjected to such treatment);[22] and, ii) at the interface, the
two classes of materials display different molecular organiza-
tion characteristics.
To identify the dominant mechanism responsible for the ob-
served differences in surface energies between the acrylates
and the silicones, representative film structures from each
class of material were subjected to X-ray photoelectron spec-
troscopy (XPS) analysis. The XPS data associated with film
structures prepared using the higher fluorosilicones (PFE9
and PFE7) revealed that the observed atomic percentages for
silicon and backbone-oxygen were significantly higher than
those expected from the stoichiometry of the bulk sample,
whereas the corresponding values for fluorine and carbon
were proportionately suppressed. Thus, for both materials,
there is a preferential distribution of the siloxane backbone
nearer to the surface, with the pendent perfluorocarbon chains
oriented towards the bulk of the sample. The surface arrange-
ments of the poly(perfluoroacrylate)s and poly(perfluoro-
methacrylate)s, PFA9, PFA7, PFMA9, and PFMA7, were
found to be diametrically opposite to those of the polysiloxane
films. Thus, the atomic percentages of the two types of back-
bone carbon, -CH2- and -CR- (R = H acrylates; R = CH3 meth-
acrylates) were significantly lower than those expected for the
bulk sample.[23,24] By contrast, the atomic percentages for fluo-
rine and oxygen, both of which are associated with the side-
chain, were mildly enhanced. Therefore, for these types of ma-
terial, the perfluorocarbon side chains segregate preferentially
at the surface. Since the lowest energy surfaces are those con-
taining perfluoroalkyl groups that are oriented to yield ex-
posed -CF3 moieties,[20] the observed surface organization
phenomena for all polymers considered are consistent with
the trends in surface energy values summarized in Table 1.
(CH2)3 (CH2)2 (CF2)n CF3
O
http://www.advmat.de Adv. Mater. 2003, 15, No. 7±8, April 17
J. Tsibouklis, T. G. Nevell/Ultra-Low Surface Energy Polymers

RESEARCH NEWS
Table 1. Advancing contact angles for water, (cL = 72.8, cLLW = 21.8, cL+ = 25.5, cL± = 25.5), diiodo- angle measurements could be obtained rou-
methane, DIM (cL = 50.8, cLLW = 50.8, cL+ = 0, cL± = 0) and ethylene glycol, EG (cL = 48, cLLW = 29,
cL+ = 1.92, cL± = 47) on acrylate and silicone film structures (Scheme 1), and corresponding surface
tinely;[21±25] film structures subjected to this
energies cS and components (cS = cSLW + 2(cS+ cS±)1/2) [14,15]. The Ra measure of surface roughness, as kind of treatment were found to exhibit su-
determined by AFM, is also given. Hysteresis values H are reproduced as appropriate. perior mechanical strength and good opti-
Contact angle,  (H) Surface energy cal clarity.[26±28]
[] [mJ m-2]
n Ra water DIM EG cSLW cS+ c S± cS
[nm] 5. Atomic Force Microscopy
poly(perfluoroalkylacrylate)s PFA (AFM) Force Measurements and
9 11.0 125 (4) 112 (16) 120 (25) 5.0 0.1 1.6 5.6 Mapping
7 9.6 117 (8) 112 (12) 108 (17) 5.0 0.1 2.3 6.1
5 5.1 114 108 108 6.1 0.0 3.6 6.4
Although contact angle goniometry is the
3 3.1 113 105 110 7.0 0.0 4.7 7.9
method of choice for the determination of
poly(perfluoroalkylmethacrylate)s PFMA
surface energies, AFM may be a more read-
9 7.13 125 (6) 109 (13) 107 (34) 5.8 0.3 0.1 6.1
7 1.17 125 (9) 104 (12) 105 (19) 7.3 0.2 0.1 7.5
ily accessible alternative and, more signifi-
5 0.41 121 104 106 7.3 0.1 0.5 7.7 cantly, is potentially capable of facilitating
3 0.29 123 103 102 7.6 0.3 0.0 7.8 the spatial mapping of surface energy at the
poly(methylpropenoxyfluoroalkylsiloxane)s PFE nanoscale.
9 3.1 109 (3) 95 (12) 94 (8) 10.6 0.17 2.1 11.8 Atomic force microscopy has been used
7 2.3 106 96 91 10.2 0.4 2.8 12.2 to measure the force of adhesion between
5 1.0 103 87 83 14.1 0.5 2.0 16.0 polymer surfaces and an uncoated Si3N4
3 0.5 105 89 79 13.1 1.3 0.7 15.1
AFM tip.[29] The work of adhesion has been
poly(alkylacrylate)s POA
related to the surface free energy of the
5 10.2 96 52 70 33.0 0.01 1.5 33.1
polymer using the Johnson, Kendall, and
poly(methylpropenoxyalkylsiloxane)s PES
Roberts (JKR) theory of adhesion me-
13 100.0 106.9 73.4 81.8 21.0 0.1 0.3 21.3 chanics.[30±32] According to this model, the
11 115.5 84.7 72.1 75.6 21.7 0.0 12.8 21.8
9 0.9 85.2 70.0 75.4 22.9 0.0 12.0 23.4
ªpull-offº force, Fad, required to separate
7 5.6 80.5 66.8 73.8 24.6 0.1 16.4 26.6 an AFM tip of radius R from a planar
5 8.2 72.2 51.6 61.2 33.3 0.1 18.5 35.2 surface is given by:
3 3.5 91.0 62.1 82.0 27.4 0.5 8.8 31.6
1 2.0 79.6 55.2 70.9 31.3 0.3 14.9 35.4 3
Fad = πRWSMT (3)
poly(diperfluoroalkylitaconate)s PFI 2
9 8.25 125(30) 111(32) 105(27) 5.2 0.6 0.0 5.5 where
7 4.35 121(14) 104(6) 104(40) 7.3 0.2 0.3 7.8
5 0.59 121(23) 102(14) 101(26) 8.0 0.3 0.1 8.3
3 0.99 120(28) 102(22) 101(22) 8.0 0.3 0.2 8.5 WSMT = γ SM + γ TM − γ ST (4)

WSMT is the thermodynamic work of adhe-

4. Film Formation and Characterization
One important aspect of all work associated with ultra-low
surface energy polymers is the identification of suitable meth-
ods for the fabrication of film structures. The fluoropolymers
reviewed here are readily soluble in a range of solvents
(CF2ClCFCl2, CF3CF(OH)CF3, 1,3-hexafluoroxylene, super-
critical carbon dioxide).[21±25] Despite their non-stick nature,
films of these materials may be deposited from the melt or
from solution onto mechanically-roughened or low surface
energy supporting substrates: hydrophobized glass, Teflon,
and/or poly(methyl methacrylate) substrates have been found
to be appropriate for the purpose.[21±25] Work with polysilox-
ane and polyacrylate materials has shown that film samples
need to be thermally annealed for prolonged periods of time,
at temperatures close to ambient, before reproducible contact
sion for separating the sample and tip; cSM
and cTM are the surface free energies of the
sample (S) and tip (T), respectively, in contact with the medi-
um M; and, cST is the interfacial surface free energy of the
two interacting solid surfaces.[33]
In preliminary studies, work of adhesion, as determined
from force±distance curves, has been correlated with indepen-
dently determined surface free energies.[34] However, consid-
erable advances in our appreciation of the factors that influ-
ence the observed AFM force±distance curves is needed
before the technique can be routinely applied to the determi-
nation of surface energies; in particular, the effects of surface
heterogeneities resulting from molecular organization phe-
nomena at the outermost atomic layers of the film struc-
tures,[35] and the implications associated with surface-rough-
ness-induced phenomena, as related to the increased area of
the contact between the probing tip and the sample,[36] need
to be considered in detail.

Adv. Mater. 2003, 15, No. 7±8, April 17 http://www.advmat.de Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 649

RESEARCH NEWS
6. Future Direction
One of the outstanding characteristics of fluorocarbon sub-
stitution in polymers is the potential for obtaining materials
with low surface energy. Much of the commercial success of
poly(dimethylsiloxane) (PDMS) and PTFE has been asso-
ciated with their use as coatings possessing surface energies
that are lower than those of the substrates, and also lower
than those of most hydrocarbon-based polymers. However,
the extent of fluorination in the molecule is critical. The low
degree of fluorination in poly(methylfluoropropylsiloxane),
the most familiar fluorosilicone, is insufficient to impart time-
independent properties, whereas the surface roughness char-
acteristics of PTFE render this polymer unsuitable for many
applications.[37±39] Just as the development of PDMS-based
additives and treatments has produced new opportunities for
organic polymers, so also will new ªultra-low surface energyº
fluoropolymers contribute to developments in conventional
low surface energy materials. Potential uses that are as diverse
as lubrication, wear control, antifouling, and antisoiling will
have weighty commercial implications.
Work to date has provided the basis for an in-depth appre-
ciation of the relationship between molecular structure and
surface energy in polymeric coating materials: a comb-like
structure with pendent fluorocarbon chains is essential. How-
ever, to facilitate the material selection process, some molecu-
lar design issues need to be investigated in more detail. In par-
ticular, questions regarding the precise nature of the
backbone (sp, sp2, sp3) and the density of side chains (number
of side chains per constitutional repeat unit) as related to film-
forming characteristics and submolecular-level surface organi-
zation phenomena need to be addressed. By considering other
types of macromolecular structures, both our appreciation of
the structure±property relationships will be refined, and a
range of materials with well-defined thermal characteristics
(Tg, Tm, degradation temperature) and mechanical properties
(hardness, flexibility, resistance to abrasion, impact strength)
will become available for employment in situations defined by
the demands of each proposed use. Finally, the development
of emulsion-based delivery systems for these polymers will
ensure accessibility and ease of application to surfaces.
± [38] J. Tsibouklis, M. Stone, A. A. Thorpe, P. Graham, V. Peters, R. Heerlien,
[1] H. Kobayashi, M. J. Owen, Trends in Polymer Science 1995, 3, 10.
[2] D. L. Schmidt, C. E. Coburn, B. M. DeKoven, G. E. Potter, G. F. Meyers,
D. A. Fischer, Nature 1994, 368, 39.
______________________
650 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Tsibouklis, T. G. Nevell/Ultra-Low Surface Energy Polymers
[3] E. F. Cuddihy, in Particles on Surfaces 1: Detection, Adhesion and Re-
moval (Ed: K. Mittal), Plenum Press, New York 1988, pp. 91±111.
[4] M. M. Tunney, S. P. Gorman, S. Patrick, Rev. Med. Microbiol. 1996, 7, 195.
[5] B. Boutevin, Y. Pietrasanta, Fluorinated Acrylates and Polyacrylates: De-
rivatives and Applications, presented at EREC, Paris 1988.
[6] L. Klinger, J. R. Griffith, C. J. N. Ball, Org. Coat. Appl. Polym. Sci. Proc.
1983, 48, 407.
[7] C. G. DeMarko, A. J. Macquade, S. J. Kennedy, Mod. Text. Mag. 1960, 2,
50.
[8] Y. Matsumoto, K. Yoshida, M. Ishida, Sens. Actuators 1998, A66, 308.
[9] B. E. Smart, in Organofluorine Chemistry: Principles and Commercial Ap-
plications (Ed: R. E. Banks), Plenum Press, New York 1994.
[10] R. G. Good, C. J. van Oss, in Modern Approaches to Wettability: Theory
and Applications (Eds: M. E. Schrader, G. Loeb), Plenum Press, New
York 1991, pp. 1±27.
[11] R. G. Good, M. K. Chaudhury, C. J. van Oss, in Fundamentals of Adhe-
sion (Ed: L. H. Lee), Plenum Press, New York 1991, pp. 153±172.
[12] S. H. Wu, Polymer Interfaces and Adhesion, Marcel Dekker, New York
1982.
[13] Y. W. Lau, C. M. Burns, J. Polym. Sci., Polym. Phys. Ed. 1974, 12, 431.
[14] M. K. Bernett, W. A. Zisman, J. Phys. Chem. 1960, 64, 1292.
[15] R. H. Dettre, R. E. Johnson Jr., J. Colloid Interface Sci. 1966, 21, 367.
[16] R. H. Dettre, R. E. Johnson Jr., J. Colloid Interface Sci. 1969, 31, 568.
[17] D. Glennon, J. R. Smith, P. A. Cox, R. Ewen, R. T. Nevell, T. G. Nevell,
J. Tsibouklis, J. Mater. Sci. 1998, 33, 3511.
[18] J. Wang, C. K. Ober, Macromolecules 1997, 30, 7560.
[19] R. A. Pullin, T. G. Nevell, J. Tsibouklis, Mater. Lett. 1999, 39, 142.
[20] M. J. Owen, Comments Inorg. Chem. 1988, 7, 195.
[21] M. Stone, T. G. Nevell, J. Tsibouklis, Mater. Lett. 1998, 37, 102.
[22] E. Barbu, R. A. Pullin, P. D. Graham, P. J. Eaton, J. R. Smith, T. G. Ne-
vell, J. D. Smart, R. J. Ewen, J. Tsibouklis, Polymer 2002, 43, 1727.
[23] J. Tsibouklis, P. D. Graham, P. J. Eaton, J. R. Smith, T. G. Nevell, J. D.
Smart, R. J. Ewen, Macromolecules 2000, 33, 8460.
[24] J. Tsibouklis, M. Stone, A. A. Thorpe, P. Graham, R. J. Ewen, T. G. Ne-
vell, Langmuir 1999, 15, 7076.
[25] M. A. McHugh, A. Garach-Domech, I.-H. Park, P. Graham, E. Barbu,
J. Tsibouklis, Macromolecules 2002, 35, 6479.
[26] P. Graham, M. Stone, A. Thorpe, T. Nevell, J. Tsibouklis, J. Fluorine
Chem. 2000, 104, 29.
[27] A. A. Thorpe, T. G. Nevell, J. Tsibouklis, Appl. Surf. Sci. 1999, 137, 1.
[28] A. A. Thorpe, S. A. Young, T. G. Nevell, J. Tsibouklis, Appl. Surf. Sci.
1998, 136, 99.
[29] J. N. Israelachvili, Intermolecular and Surface Forces, 2nd ed., Academic
Press, London 1992.
[30] K. L. Johnson, K. Kendall, A. D. Roberts, Proc. R. Soc. London Ser. A
1971, 324, 301.
[31] A. Noy, D. V. Vezenov, C. M. Lieber, Annu. Rev. Mater. Sci. 1997, 27, 381.
[32] A. Kawai, H. Nagata, H. Morimoto, M. Takata, in Surface Modification
Technologies VII (Eds: T. S. Sudarshan, K. Ishizaki, M. Takata, K. Kama-
ta), Sanjo, Niigata, Japan 1993.
[33] J. P. Cleveland, S. Manne, D. Bocek, P. K. Hansma, Rev. Sci. Instrum.
1993, 64, 403.
[34] T. Abbis, G. Collins, R&D (Reed) 1995, 37, 57.
[35] P. J. Eaton, P. Graham, J. R. Smith, J. D. Smart, T. G. Nevell, J. Tsibouklis,
Langmuir 2000, 16, 7887.
[36] P. J. Eaton, J. R. Smith, P. Graham, J. D. Smart, T. G. Nevell, J. Tsibouklis,
Langmuir 2002, 18, 3387.
[37] A. G. Gristina, Science 1987, 237, 1588.
J. R. Smith, K. L. Green, T. G. Nevell, Biomaterials 1999, 20, 1229.
[39] P. Graham, I. Joint, T. G. Nevell, J. R. Smith, M. Stone, A. Thorpe, I. Joint,
J. Tsibouklis, Biofouling 2000, 16, 289.
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