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Durable Antifog Films from Layer-by-Layer Molecularly Blended

Hydrophilic Polysaccharides
Nurxat Nuraje,† Ramazan Asmatulu,†,§ Robert E. Cohen,*,‡ and Michael F. Rubner*,†
†
Department of Materials Science and Engineering, and ‡Department of Chemical Engineering,
Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139,
United States, and §Department of Mechanical Engineering, Wichita State University, Wichita,
Kansas 67260, United States

Received September 19, 2010. Revised Manuscript Received November 10, 2010

Mechanically durable, long-lasting antifog coatings based on polysaccharides were developed using a layer-by-layer
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(LBL) assembly process. The unique properties of these coatings are a result of a molecular-level blending of the
polysaccharides, with multilayers containing chitosan and carboxymethyl cellulose providing the best overall properties.
The antifog properties resulted from a strong interaction between the polar and H-bonding elements of the assembled
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polymers and water molecules and the concomitant formation of thin films of water. Environmental scanning electron
microscopy (ESEM) studies confirmed that fogging coatings are decorated with light scattering, micrometer-sized
droplets of water whereas antifogging coatings remain droplet free. To improve the mechanical durability of the
multilayer films on substrates, the surface was modified via self-assembly of epoxy-functionalized silane molecules.
Cross-linking chemistry was then applied to improve the mechanical robustness of the LBL films on various surfaces.
These films were characterized using several techniques: optical profilometery (PL), spectroscopic ellipsometry (EL),
contact angle goniometry (CA), and atomic force microscopy (AFM). The antifog properties of the films were evaluated
by several tests under different environmental conditions. This work demonstrates that the unique water-adsorbing
properties of polysaccharides can be exploited to create permanent antifog properties, which may be useful for various
applications.

1. Introduction although condensation still occurs, the surface remains optically

The fogging of surfaces due to the condensation of light-scattering clear. The key to this approach is the use of materials that strongly
microscopic droplets of water under a variety of environmental interact with water molecules and/or have a high capacity for
conditions continues to be problematic both in day-to-day life adsorbing water. Hydrophilic polymeric systems containing poly-
and in many technological applications.1-3 Currently, there (ethylene glycol) and poly(vinyl alcohol), for example, are often
remains an unmet need for long-lasting and mechanically robust utilized in antifog formulations.10 It is well established that many
antifog coatings that can operate under a variety of different naturally occurring polymers such as cellulose and various
fogging challenges2,4,5 (e.g., temperature and humidity). A num- hydrophilic polysaccharides11-13 strongly adsorb water in var-
ber of different approaches have been put forth to alleviate the ious forms, including nonfreezable forms of water. Given the
fogging problem, including the exploitation of surfaces with superior water-absorbing characteristics of these materials and
extreme wetting characteristics such as superhydrophobicity5,6 their ability to support multiple forms of water (freezing and
or superhydrophilicity.2,3 More often than not, however, these nonfreezing), they are ideal candidates for antifog coatings. The
textured, nanoporous, or light-activated surfaces suffer from processing of these materials into optical-quality thin-film coatings,
issues such as short lifetimes, excessive fouling, susceptibility to however, is difficult, particularly if they are to be blended with
high-humidity environments, and poor mechanical durability.2,4,7 other synthetic polymers or polysaccharides to achieve optimum
Hydrophilic surfaces with advancing water droplet contact coating characteristics and mechanical durability.
angles of less than 40° are often explored as antifog coatings due In this work, we demonstrate that hydrophilic polysaccharides
to their potential ability to rapidly spread condensing water droplets such as chitosan, alginate, hyaluronic acid, and carboxymethyl
into a uniform, non-light-scattering film of water.1,8,9 In this case, cellulose can be blended at the molecular level to produce optical-
quality thin films with excellent, long-lasting antifog performance.
*Corresponding authors. E-mail: [email protected] (M.F.R.), recohen@ Molecular-level blending of the polysaccharides, including blends
mit.edu (R.E.C.). with synthetic polymers containing ethylene glycol segments, was
(1) Howarter, J. A.; Youngblood, J. P. Macromol. Rapid Commun. 2008, 29, achieved via the well-established layer-by-layer assembly technique.14
455–466.
(2) Cebeci, F. C.; Wu, Z.; Zhai, L.; Cohen, R. E.; Rubner, M. F. Langmuir 2006, Environmental scanning electron microscopy (ESEM) studies
22, 2856–2862.
(3) Wang, R.; Hashimoto, K.; Fujishima, A.; Chikuni, M.; Kojima, E.;
Kitamura, A.; Shimohigoshi, M.; Watanabe, T. Nature 1997, 388, 431–432. (10) See US Patents 4478909 (1984), 5075133 (1991), and 5804612 (1998).
(4) Gemici, Z.; Schwachulla, P. I.; Williamson, E. H.; Rubner, M. F.; Cohen, (11) Schartel, B.; Wendling, J.; Wendorff, J. H. Macromolecules 1996, 29, 1528–
R. E. Nano Lett. 2009, 9, 1064–1070. 1534.
(5) Gao, X.; Yan, X.; Yao, X.; Xu, L.; Zhang, K.; Zhang, J.; Yang, B.; Jiang, L. (12) Fringant, C.; Desbri
eres, J.; Milas, M.; Rinaudo, M.; Joly, C.; Escoubes, M.
Adv. Mater. 2007, 19, 2213–2217. Int. J. Biol. Macromol. 1996, 18, 281–286.
(6) Cheng, Y.-T.; Rodak, D. E. Appl. Phys. Lett. 2005, 86, 144101. (13) Radloff, D.; Boeffel, C.; Spiess, H. W. Macromolecules 1996, 29, 1528–
(7) Gemici, Z.; Shimomura, H.; Cohen, R. E.; Rubner, M. F. Langmuir 2008, 24, 1534.
2168–2177. (14) Decher, G.; Schlenoff, J. B. Multilayer Thin Films: Sequential Assembly of
(8) Grosu, G.; et al. J. Phys. D: Appl. Phys. 2004, 37, 3350. Nanocomposite Materials; Wiley-VCH Verlag GmbH & Co.: Weinheim, Germany,
(9) Briscoe, B. J.; Galvin, K. P. Sol. Energy 1991, 46, 191–197. 2003.

782 DOI: 10.1021/la103754a Published on Web 12/16/2010 Langmuir 2011, 27(2), 782–791
Nuraje et al. Article

reveal directly that these coatings are able to effectively spread An experimental description of this test was discussed in a
condensing water droplets into uniform sheets. The mechanical previous study.2 In test (b), for quick evaluation of the antifog
durability of the resultant coatings was further improved with easily performance of the coatings, a simple aspirating/breathing test
introduced surface modification and cross-linking chemistry. was conducted on the sample. The boiling test (c) was established
mimicking the European Standard test (EN168). In this test, an
2. Experimental Section Erlenmeyer flask containing boiling water was placed on top of
written letters. The written letters were observed through the other
2.1. Materials. The following materials were purchased from side of the film by the naked eye after the film was exposed to the
Sigma-Aldrich: carboxymethyl cellulose (CMC) (Mw=250 000), steam of the Erlenmeyer flask. The visibility of the letter at the
low-molecular-weight chitosan (CHI, Mw = 50 000), glutaraldehyde bottom of the Erlenmeyer flask was evaluated for the degree of
(25% solution, Mw=100.12), poly(ethylene imine) (PEI) (branched, antifog. In the cold-fog test (d), the substrates coated with multi-
Mn =10 000, Mw =25 000), 2-(N-morpholino)ethanesulfonic layers were placed in a refrigerator (4 °C) for several hours and
acid monohydrate (MES), and sodium chloride. Poly(acrylic then placed in a humidity chamber (37 °C and 80% humidity) or
acid) (PAA) (25% aqueous solution, Mw = 90 000 g/mol) was on the top of a Erlenmeyer flask containing steaming water.
supplied by Polysciences (Warrington, PA). Gelest was the source 2.2.4. Cross-Linking of the Multilayers. The glass substrate
for (3-glycidoxypropyl)trimethoxysilane (GPTMS). Glass micro- was first sonicated in water for 5 min and cleaned in oxygen
scopy slides with 7.52.50.1 cm dimensions were obtained from plasma for 2 min at 120 mTorr or treated in a piranha solution for
VWR (Cat. No. 48300-047). Bare polycarbonate was provided by 30 min at 80 °C. The cleaned substrate was immediately incubated
Teijin-Kasei Corp. Thermo Scientific supplied 1-ethyl-3-(3-(di- with an anhydrous toluene solution of 1% (3-glycidoxypropyl)-
methylamino)propyl)carbodiimidehydrochloride (EDC) and N- trimethoxysilane overnight and then rinsed with pure toluene.
hydroxysulfosuccinimide (NHS). Asylum Research was the source Toluene can be replaced by other anhydrous organic solvents such
for AFM (MFP3D) and tips (AC240TS, AC200TS), which were as chloroform and hexane. All of the above experiments were
utilized to scratch the film using the nanolithography mode.15 A conducted in a dry glovebox. The dried substrate was immersed in
polishing cloth (DP-NAP) with adhesive backing was purchased a 0.01 M aqueous solution of branched PEI (pH=9) for at least
from STRUERS Inc. Our laboratory synthesized poly(acrylic 4 h and subsequently rinsed with water. Next, multilayers of CHI/
acid)-graft-poly(ethylene glycol) (PAA-g-PEG), following proce- CMC were assembled onto the PEI-modified substrate at pH=4.
dures in the literature.16,17 Deionized (DI) water was used in all The substrate with the assembled multilayer of CHI/CMC was
aqueous solutions and rinsing procedures. then immersed into a 0.05 M MES buffer (pH = 5), including
2.2. Methods. 2.2.1. Thin-Film Assembly. The LBL as- 200 mM EDC and 50 mM NHS,18 for 30 min and subsequently
sembly of polymer/polymer systems on glass and polycarbonate immersed into a 1X PBS buffer for 20 min. The cross-linked
slides was performed using a Stratosequence VI spin dipper multilayer of CHI/CMC on the glasslike substrate was then rinsed
(Nanostrata Inc.) controlled by StratoSmart v6.2 software. Dip- with water. The antifog coatings were not only chemically bonded
ping time for polymers was 10 min, followed by three rinses (one 2 between layers but also chemically bonded to the functiona-
min rinse followed by two 1 min rinses) using DI water of the same lized substrate surface. To further cross-link the multilayers, the
pH as the preceding polymer solution. The concentration of CHI coating was immersed in an aqueous solution of 2.5% glutar-
and CMC was 0.1 wt %. The pHs of the polymer solutions and aldehyde at pH=9 and 30 °C for 45 min. The substrate was then
rinsing water were adjusted with either 0.1 M HCI or 1 M NaOH. rinsed with DI water.
Glass substrates were degreased in a 3% solution of Micro90 2.2.5. Mechanical Properties. Mechanical integrity of the
under sonication for 20 min, and the substrates were subsequently films was evaluated by several methods, including the following:
sonicated in 1 M NaOH for another 20 min. Finally, the glass (a) ASTM D3363 pencil hardness test, (b) home-built rotary cloth
substrates were sonicated in deionized water (DI) water for 5 min abrasion test,7 (c) KIMWIPE test, (d) qualitative cloth-sponge
and blown dry with air. Polycarbonate substrates were pretreated rubbing test, (e) crosshatch adhesion test (i.e., Scotch tape test),
with oxygen plasma (PDC-32G, Harrick Scientific Products, Inc.) and (f) AFM nanolithography-controlled scratching test. In the
for 30 s at 400 mTorr on both sides before building the multilayers. pencil hardness test, the coated glass substrate was placed under
2.2.2. Characterization. Thickness measurements of assembled the tip of a pencil, and the pencil holder was moved in one direction.
multilayers on substrates were performed by a Tensor P16 surface The force applied to the pencil tip came from a 750 g static load.
profilometer (PL) using a 2 μm stylus tip and 2 mg stylus force. The scratched regions were evaluated by optical microscopy. In
The topographical image of the multilayer was collected using a the abrasion test, changes in optical transmittance of the film after
Nanscope IIIa, Dimension 3000 AFM microscope (Digital In- rotary wiping with a standardized cloth were correlated with
struments, Santa Barbara, CA) in the tapping mode. Variable- mechanical damage using experimental methods. Data analysis
angle spectroscopic ellipsometry (EL) was employed to measure protocols were explained in detail in the previous study.7 In the
the thickness and refractive index of the film on polycarbonate present study, we challenged the coatings with the maximum
substrates. Contact angle measurements were carried out with a available level of normal stress (100 kPa) in the abrasion testing.
VCA-2000 contact angle system (AST Products, Inc., Billerica, The cloth-sponge rubbing test included three different levels of
MA). Contact angle values were calculated from dynamic video challenges. The coating was first wetted with water or soap
files captured at 60 frames/s using the software VCA Optima XE solution (2% MICRO-90 solution from International Products
Version 1.90 provided by the manufacturer. Corp.) and rubbed with a cloth (ANTICON, Lot #5562) or a
2.2.3. Antifog Tests. Antifog properties were evaluated cellulose sponge under three different conditions. In the first test,
through four separate testing protocols: (a) humidity chamber the wet coating was rubbed with a wet sponge 10 times. In the
test, (b) aspiration test, (c) boiling test, and (d) cold-fog test. In test second test, the wet coating was rubbed with a wet cloth 10 times.
(a), the humidity within the chamber was controlled with an In the third test, the wet coating was rubbed with a dry cloth 10
ultrasonic humidification/ventilation system. A slide coated with times. The last test was considered to be the most rigorous test of
an antifog multilayer was evaluated by recording an image of the mechanical strength among the cloth-sponge tests. In the cross-
slide at 37 °C and 80% humidity in the chamber at various times. hatch adhesion test, 3M tape was first placed on the top of the film
for a couple of seconds and then removed from the film. The
(15) Nuraje, N.; Banerjee, I. A.; MacCuspie, R. I.; Yu, L.; Matsui, H. J. Am. damaged areas were evaluated. This technique shows the adhe-
Chem. Soc. 2004, 126, 8088–8089. sion degree of the film onto the substrate.
(16) Asatekin, A.; Kang, S.; Elimelech, M.; Mayes, A. M. J. Membr. Sci. 2007,
298, 136–146.
(17) Irvine, D. J.; Mayes, A. M.; Griffith, L. G. Biomacromolecules 2001, (18) Nuraje, N.; Mohammed, S.; Yang, L.; Matsui, H. Angew. Chem., Int. Ed.
2, 85–94. 2009, 48, 2546–2548.

Langmuir 2011, 27(2), 782–791 DOI: 10.1021/la103754a 783

Article Nuraje et al.

Table 1. Antifog Properties of Various Multilayers on Glass Slides

climate chamber Erlenmeyer steam
multilayer test test Huff test cold-fog test thickness (nm) refractive index

[CHI/CMC]15 antifog antifog antifog antifog ∼100 1.54

[CHI/CMC]15 Cross-linked antifog antifog antifog antifog ∼100 1.44
[CHI/PAA]15 fogging fogging fogging fogging >100 1.54
[CHI/PAA-co-PEG]10 25% PEG in copolymers fogging fogging fogging fogging >100 1.54
[CHI/PAA-co-PEG]7 PEG ∼37% in copolymers antifog antifog antifog antifog ∼100 1.54
[PAH/SPS]60 a
fogging fogging fogging fogging ∼100 1.54
(PAH/PAA)10b fogging fogging fogging fogging ∼100 1.54
[CHI/AG]15c antifog antifog antifog antifog >100 1.54
d
[CHI/HA]15 antifog antifog antifog antifog >100 1.54
a
[PAH/SPS] assembled at pH=3. b pHs of PAH and PAA were respectively 7.5 and 3.5 for the assembly of the films. c Concentration and pH of AG are
0.02% and 4. d Concentration and pHs of HA(Mw: 650K) and CHI(medium Mw) respectively are 0.1% and 4.

In the AFM nanolithography scratching test,15,18 various spring

constant tips were applied to scratch the films with both horizontal
and vertical lines via a nanolithography program. The scratched
lines were evaluated using section analysis software. All of the
experiments were performed using an Asylum MFP AFM. The
applied force for scratching the films was found by calibrating the
force curve of specific tips to bare glass substrate. After the spring
constant of the specific tip was determined, voltage equal to the
force needed was set as the set point for the AFM nanolithogra-
phy program. Thus, this program directed the tip to move in
certain directions with specific applied forces.
2.2.6. Environmental Scanning Electron Microscopy. ESEM
connected to a DVD recording system (Philips) was used to
observe in situ water droplet growth on the surface of the LBL
films. The temperature and humidity of an environment were
controlled during ESEM studies. The experiments were conducted
at 15 °C with a humidity range of 90-95%. The movies were
recorded as soon as the environment in the ESEM chamber began
getting humid.

3. Results and Discussion

3.1. CHI/CMC Multilayer Assembly. In order to create
multilayer thin films with permanent antifog properties, we
explored the use of various hydrophilic polysaccharides, with Figure 1. Turbidity results of CHI/CMC system at various salt
the idea that such polymers have a number of functional elements concentrations and pH values. Turbidity was measured 10 min
after mixing the polyanion and the polycation.
that have the ability to interact strongly with water molecules
through, for example, the formation of hydrogen bonds. The ∼2.5 or higher. At pH = 1.5, essentially only soluble polymer
blending of these materials at the molecular level was achieved by chains/complexes exist in solution (no turbidity), suggesting that
using a layer-by-layer assembly technique. Table 1 summarizes multilayer assembly at this pH would be prohibited.19 As the
the various polymer combinations examined including polyelec- solution pH increases, turbidity increases significantly as a result
trolyte multilayers assembled with typical synthetic polyanions of an increased ionization of the CMC chains and the formation
and polycations. As will be discussed, the best antifog capability of insoluble polymer complexes. As pH = 7 is approached, the
was realized when specific oppositely charged polysaccharides, level of turbidity further increases due to polymer solubility
such as hyaluronic acid (HA), alginate (AG), chitosan, and problems with the CHI. Thus, the multilayer assembly of this
carboxymethyl cellulose, were assembled into thin-film coatings. system is best accomplished in the pH range of 3-6, with pH=4
Notably, it was found that multilayer films assembled from being the preferred assembly pH.
chitosan (CHI) and carboxymethyl cellulose (CMC) produced To determine how salt concentration influences the growth
the best overall properties; hence, we will focus on the assembly behavior of the CHI/CMC system, solutions with between 0 and
and physical properties of this multilayer system. 0.25 M NaCl were used. The thicknesses of 30-bilayer coatings
In initial screening studies, the film growth of the CHI/CMC assembled on glass substrates at different salt concentrations were
multilayer system was evaluated at different pH solutions (pH = investigated. Salt concentrations of 0, 0.1, and 0.25 M resulted in
1.5, 4, and 6). Because of the instability of chitosan at pH=7 and total film thicknesses of 531, 1630, and 19 nm, respectively ((10%).
above, we only investigated the film growth behavior up to pH 6. The much lower bilayer thickness of the film prepared in 0.25 M
The total film thickness of a 30-bilayer film of CHI/CMC assembled salt solutions suggests that multilayer assembly under these condi-
at pH=6 (215 nm) was less than that of a film assembled at pH=4 tions is restricted. Sukhishvili and co-workers have shown that
(530 nm). With a solution of pH=1.5, no film formation occurred soluble polymer complexes can be formed during multilayer
on the substrates. To understand this pH dependence, the assembly due to local concentration effects.19-21 Alternatively,
turbidity of mixed solutions of these two polymers was measured Mjahed et al.22 demonstrated that turbidity diagrams can be used
as a function of pH and salt concentration. The data in Figure 1
reveal that turbid solutions, an indication of the formation of (19) Sukhishvili, S. A.; Kharlampieva, E.; Izumrudov, V. Macromolecules 2006,
insoluble polymer complexes, only occur when the solution pH is 39, 8873–8881.

784 DOI: 10.1021/la103754a Langmuir 2011, 27(2), 782–791

Nuraje et al. Article

Figure 2. Film growth of the CHI/CMC system assembled at

pH = 4 on glass substrates (units of the slope are nm/bilayer).

to predict polyelectrolyte multilayer deposition on surfaces. To

test this hypothesis, the two polymers were mixed at a 25:1 ratio in
a 0.25 M NaCl aqueous solution. The resultant clear solution
demonstrated the formation of a water-soluble complex. In con-
trast, turbid solutions were formed when the polymers were mixed
at this same ratio in solutions containing no salt or 0.1 M salt.
On the basis of the above screening results, CHI/CMC films
Figure 3. Photo images of CHI/CMC coatings on glass and poly-
were assembled at pH = 4 without the addition of salt (similar carbonate taken after exposure to high humidity in climate cham-
antifog properties resulted when 0.1 M salt was included in the ber for 10 s; 20 bilayers of CHI/CMC on (A) glass, (B)
LbL production of the films) and characterized by profilometer, polycarbonate, (C) left lens of a safety goggle. Yellow lined area
AFM, contact angle measurements, and ellipsometry. Figure 2 indicates where coating was applied.
shows the film growth of the CHI/CMC system on a glass
substrate as a function of the number of deposited bilayers environmental chamber after incubation at room temperature,
(polycation plus polyanion). Two linear regions can be seen: the (b) using a basic room temperature breath test (Huff test), and (c)
first region is between 0 and 15 bilayers, while the second region is placing the sample over boiling water after incubation at room
between 15 and 30 bilayers. The thicknesses of 10- and 30-bilayer temperature. The results of these various test are summarized in
films were around 23 and 570 nm, respectively. Similar growth Table 1. Similar results were obtained when samples were first
trends were found when polycarbonate was used as the support- cooled to T=4 °C and then subjected to these various fogging
ing substrate. When the number of bilayers of CHI/CMC was challenges.
lower than 15, the growth behavior of the multilayer film was First, it should be noted that although typical multilayers
different from that of CHI/CMC with 15 or more bilayers. Similar fabricated from synthetic polyelectrolytes, such as SPS, PAA, and
film growth behavior has been observed with other polysacchar- PAH, are generally hydrophilic, they do not exhibit acceptable
ide multilayers.23,24 Picart et al.23 explained that the multilayer antifogging behavior: extensive fogging occurs within seconds of
buildup of hyaluronan/chitosan is comprised of two distinct exposure to a fogging environment. In contrast, multilayers fabri-
stages. The first stage is characterized by isolated islet growth, cated from hydrophilic polysaccharides, such as hyaluronic acid,
whereas the second stage involves a more continuous film con- alginate, chitosan, and carboxymethylcellulose, provide excellent
struction. They also reported that film thickness increased with antifogging capability under a variety of different fogging chal-
increasing salt concentration in the deposition solutions. AFM lenges. In the case of the optimized CHI/CMC multilayers
analysis revealed that the multilayers were relatively smooth with (assembly pH=4.0, no added salt), excellent antifog ability was
rms roughness values of 20-, 30-, 40-, and 50-bilayer films being observed on films assembled on both glass and polycarbonate
less than 8 nm. substrates (see Figure 3). In addition, similar antifog performance
3.2. Antifog Properties of Multilayer Films. The antifog was observed in multilayers with either CMC or chitosan as the
properties of various polyelectrolyte multilayers were examined last deposited layer. To achieve this high level of antifog perfor-
under a variety of different fogging conditions. These included the mance, a minimum thickness of about 20 nm is required for the
following: (a) exposing the film to 80% humidity at 37 °C in an multilayer film. For multilayer films of lower thickness, incomplete
coverage of the substrate surface compromises the antifog effect.
(20) Kovacevic, D.; van der Burgh, S.; de Keizer, A.; Cohen Stuart, M. A. 3.3. Structural/Molecular Requirements Needed for Antifog
Langmuir 2002, 18, 5607–5612. Multilayers. On the basis of the excellent antifog behavior of
(21) Kabanov, V. A.; Zezin, A. B. Pure Appl. Chem. 1984, 56, 343.
(22) Mjahed, H.; Voegel, J.-C.; Chassepot, A.; Senger, B.; Schaaf, P.; Boulmedais,
CHI/CMC multilayer coatings, we hypothesized that specific
F.; Ball, V. J. Colloid Interface Sci. 2010, 346, 163–171. polar groups in the backbone and side chains of these hydrophilic
(23) Picart, C.; Mutterer, J.; Richert, L.; Luo, Y.; Prestwich, G. D.; Schaaf, P.; polymers interact strongly with water molecules via hydrogen-
Voegel, J.-C.; Lavalle, P. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 12531–12535.
(24) Richert, L.; Lavalle, P.; Payan, E.; Shu, X. Z.; Prestwich, G. D.; Stoltz, bonding and related dipole interactions, ultimately leading to the
J.-F.; Schaaf, P.; Voegel, J.-C.; Picart, C. Langmuir 2004, 20, 448–458. formation of a continuous, non-light-scattering layer of water.

Langmuir 2011, 27(2), 782–791 DOI: 10.1021/la103754a 785

Article Nuraje et al.

Figure 4. Humidity chamber tests of 10-bilayer films of chitosan/PAA-g-PEG (25% PEG) at 37 °C and 80% relative humidity for (A) 10 s
and (B) 20 s.

Thus, the typical polymer-paired, hydrophilic ionic groups pre- with the surface of the material. It has been suggested that
sent in electrostatically assembled multilayers are not sufficient to hydrophilic surfaces with advancing contact angles less than 40°
impart antifogging behavior; strong hydrogen-bonding groups, should exhibit antifog behavior.1,9
such as hydroxyl and/or ether groups, are also needed. To test this In recent work, however, we found that for nanoporous coat-
hypothesis, we assembled and tested multilayers containing ings contact angles less than about 7° were needed to achieve
chitosan and PAA molecules with different amounts of a como- acceptable antifog behavior.2 Thus, a clear correlation between
nomer containing poly(ethylene glycol) segments. PEG is non- the antifog capability of a coating and its water droplet advancing
ionic and is known for its ability to interact strongly with water contact angle does not always exist.
molecules.25 The advancing contact angles of the antifogging CHI/CMC
PEG-co-PAA copolymers were synthesized with an increasing and CHI/PAA-co-PEG (37%, 48%) multilayers were measured
amount of PEG content in the copolymer and assembled with to be between 20° and 40°. In a previous paper, the contact angle
chitosan into multilayers. Multilayers assembled from CHI/PAA reported for multilayers of HA/CHI24 was 25°. The advancing
and CHI/PAA-co-PEG (25%) did not exhibit antifog behavior contact angles of the fogging multilayers of PAH/SPS, PAH/
(Table 1 and Figure 4). However, when the PEG amount in the PAA, CHI/PAA, and CHI/PAA-g-PEG (25%) were in the range
copolymer reached about 37%, excellent antifog behavior was of 30°-90°. For all multilayers, including those that did not
observed (Table 1 and Figure 5). Likewise, multilayer films exhibit antifog properties, the receding contact angles were always
assembled with PAA copolymers containing 50% and 75% close to zero. For the most part, for these dense (not nanoporous)
PEG content exhibited excellent antifog performance. These multilayers, it appears that the general rule of needing a contact
results are consistent with the hypothesis that strong water- angle less than 40° to produce antifog behavior holds true. We do
interacting functional groups are needed in addition to ionic note, however, that exceptions to this rule were observed.
bonds to create a multilayer coating with antifogging capability. 3.4. Kinetics of Water Droplet Formation. It is generally
Hydrophilic polysaccharides and synthetic polymers rich in accepted that hydrophilic coatings inhibit fogging by preventing light-
alcohol groups and ethylene glycol units are known to exhibit the scattering water droplets from forming on a surface (Figure 6).
ability to imbibe large amounts of water and are often used in Water in this case spreads across the surface forming a “trans-
applications that exploit this effect.26,27 In addition, solid-state parent sheet”; hence, although water has condensed onto the
NMR and DSC studies11,12 of water interactions in cellulose and surface, its presence is not visually detectable. Experimental proof
poly(vinyl alcohol) blends have shown that water molecules form of this effect is oftentimes provided by a simple visual observation
hydrogen bonds with the hydroxyl, oxygen, and carboxyl groups of a substrate exposed to steaming water. In this experiment,
of the polysaccharide repeat unit. In the case of CMC, one rapid uniform wetting of the surface is taken as proof that water
repeating unit can form hydrogen bonds with five to nine water sheeting has occurred. To provide a more direct measurement of
molecules.12 water droplet formation on surfaces, we developed an in situ
One possible measure of the level of interaction of water with a ESEM technique that allows for the probing of a surface at a
material is the advancing contact angle a water droplet makes much higher resolution. Grosu et al.8 also studied fog-droplet
formation using optical microscopy and examined the relation-
€
(25) Ozdemir, C.; G€uner, A. J. Appl. Polym. Sci. 2006, 101, 203–216. ship between the size of fog droplets and contact angles.
(26) Mikolajczyk, T.; Woowska-Czapnik, D.; Bogun, M. J. Appl. Polym. Sci.
2008, 107, 1670–1677. ESEM measurements were made by exposing samples held at
(27) Dai, M.; Zheng, X.; Xu, X. J. Biomed. Biotechnol. 2009, 2009, 1–8. 15 °C to humidity levels between 90% and 95%. Images were

786 DOI: 10.1021/la103754a Langmuir 2011, 27(2), 782–791

Nuraje et al. Article

Figure 5. Humidity chamber tests of 10-bilayer films of chitosan/PAA-g-PEG (37% PEG) at 37 °C and 80% humidity for (A) 10 s and (B) 20 s.

Figure 6. Scheme illustrating antifog and fogging mechanisms on different polyelectrolyte films: (A) ESEM image of water droplets formed
on PAH/SPS film; (B) simple cartoon of water droplets on regular polyelectrolyte films such as PAH/SPS; (C) ESEM image of CHI/CMC 20-
bilayer antifog coating after exposure to 90% humidity (note the lack of discernible water droplets); (D) simple cartoon showing a water film
forming on antifog film; (E) water molecules interacting with dense polar groups on polysaccharide.

recorded after the introduction of humid air for half an hour. As were observed to form around defect areas. This underscores the
shown in Figure 7 (and movies in Figure S.1, Supporting importance of creating uniform, defect-free coatings for antifog
Information), no water droplets were observed to form on any applications.
multilayer films that exhibited excellent antifog properties. In In sharp contrast, water droplet formation was clearly ob-
these cases, samples remained free of detectable features throughout served on all multilayer films that were not antifogging (PAH/
the entire experiment. Sometimes, however, large water droplets SPS, PAH/PAA, CHI/PAA, etc.). The growth of water droplets

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Article Nuraje et al.

Figure 7. ESEM study of two different coatings at 15 °C and humidity 90%-95% after exposure for 15 s: (A) 80 bilayers of PAH/SPS
coating on glass; (B) magnified region of PAH/SPS coating; (C) 20 bilayers of CHI/PAA-co-PEG(37%) on glass; (D) magnified region of
CHI/PAA-co-PEG(37%) film.

with time on fogging multilayer films is presented in Figure 8. In

the case of the PAH/SPS multilayer film, water droplets ranging
in size from a few hundred nanometers to several micrometers
formed within about 10-20 s of exposure to the humid environ-
ment. These sized water droplets are capable of scattering visible
light. The average water droplet size was found to be typically less
than 10 μm after the full 30 min exposure to the humid environ-
ment. A statistical analysis of the average number of droplets
per mm2 observed after 10 s exposure to the humidity is found in
Figure 9. The water droplet density, at least 10 000 droplets
per mm2, was found to be high in all of the fogging polyelectrolyte
multilayers. From the ESEM study, it can be concluded that
fogging is indeed the result of the formation of a densely packed
collection of water droplets of sufficient size to scatter visible light.
3.5. Durability of CHI/CMC Multilayer Films. The util-
ity of any antifog coating is ultimately determined by the stability
of the antifogging effect and the mechanical durability of the
coating. In the former case, we found that antifog coatings based
Figure 8. Water droplet growth (observed for 10 min) versus time
on multilayers of CHI/CMC retain their antifog properties in a (seconds): (A) [PAH/SPS]80, (B) [CHI/CMC]15, (C) [PAH/PAA-
normal laboratory environment for at least a few years. In co-PEG(25%)]20, and (D) [PAH/PAA]16.
addition, CHI/CMC films can be stored in a humidity chamber
(37 °C, 80% humidity) for weeks at a time without losing their however, do not retain their antifogging functionality after exposure
antifogging capability. Previously, we reported that excellent to the humidity chamber for times as short as a few days. The
antifog coatings can be obtained from nanoporous polyelectro- most likely cause of the loss of antifogging properties is capillary
lyte multilayers containing silica nanoparticles.2 These coatings, condensation of water into the nanopores and subsequent reaction

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Nuraje et al. Article

of the silica nanoparticles with water.4 Thus, the CHI/CMC The films retained excellent optical properties, even after being
antifog films offer greater stability in those applications that require abraded for 60 min at this load. For a comparison, identical
prolonged exposure to warm, highly humid environments. abrasion tests were also conducted on bare polycarbonate sub-
Five different tests were performed to determine the mecha- strates, and the results are shown in Figure 10. Bare polycarbo-
nical durability of CHI/CMC multilayer films on glass substrates nate substrates are readily damaged by this testing protocol. The
as described in the Experimental Section. As-assembled CHI/ CHI/CMC films are mechanically more robust than as-prepared
CMC films with either 15 or 30 bilayers were tested. nanoparticle containing multilayers and bare polycarbonate
In the case of the KIMWIPE test, no visible scratches were systems.7 In the same abrasion test (100 kPa and 60 min
observed after testing. However, as-assembled films were easily duration), as-assembled nanoparticle multilayers lost more than
removed by rubbing with sponges and cloths soaked in a soap 4% transmittance. In contrast, the as-assembled polymer system
solution. In the pencil hardness test, all of the as-assembled CHI/ showed no loss of transmittance.
CMC films achieved a 1H pencil hardness, which is comparable to
a polymer like PMMA.28 Abrasion testing (Figure 10) revealed
that as-assembled CHI/CMC films on glass substrates exhibit no
loss in transmission after abrasion testing under a 100 kPa load.

Figure 10. Optical transmittance of CHI/CMC films on polycar-

bonate before and after grinding at 100 kPa stress. Blue line
represents the transmittance of polycarbonate before abrasion
testing. Yellow line represents the transmittance of polycarbonate
Figure 9. Water droplet population (number of water droplets per after abrasion testing. Green line represents the transmittance of
mm2) on different films: (A) [PAH/PAA]16, (B) [CHI/PAA]20, (C) 30-bilayer CHI/CMC-coated polycarbonate before abrasion test-
[PAH/PAA-co-PEG(25%)]20, (D) [PAH/SPS]80, and (E) [CHI/ ing. Red line represents the transmittance of this film after abrasion
CMC]15. testing.

Figure 11. Chemical modification scheme of glass substrate using self-assembly process involving epoxysilane and subsequent cross-linking
scheme for the multilayer.

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Article Nuraje et al.

Figure 12. AFM and SEM images of 20-bilayer as-assembled and cross-linked CHI/CMC films on a glass substrate. (A) AFM image of 20-
bilayer as-assembled CHI/CMC film. (B) AFM image of 20-bilayer cross-linked CHI/CMC film. (C) Side-view SEM image of 20-bilayer as-
assembled CHI/CMC film. (D) Side-view SEM image of 20-bilayer cross-linked CHI/CMC film.

Although the mechanical durability of as-assembled films may that the dense multilayer film had become nanoporous after
be sufficient for some applications, it is clearly not at the level cross-linking. Ellipsometry further confirmed the fact that
needed for more demanding environments. To enhance the cross-linking induced nanoporosity; the refractive index of the
mechanical robustness of the CHI/CMC antifog coatings, chem- as-assembled CHI/CMC multilayer is 1.54 and drops to 1.44 after
istry was introduced to improve both the adhesion of the coating cross-linking. Thus, the superhydrophilicity of the cross-linked
to the substrate and the mechanical durability of the multilayer CHI/CMC multilayer is a result of a nanoporous state, as was
(see Figure 11). In the former case, a glass substrate was first observed with nanoporous nanoparticle multilayer coatings.2
chemically modified by forming covalent bonds between an Cross-linked nanoporous (CMC/CHI)15.5 coatings on glass
epoxysilane compound (3-glycidoxypropyl)trimethoxysilane and substrates were evaluated by the mechanical tests previously
the hydroxyl groups on the substrate surface. Branched poly- mentioned. The KIMWIPE and wet cloth/sponge tests revealed
(ethylenimine) was then exposed to the epoxy-functionalized surface no visible scratches. The pencil hardness test indicated the film
for reaction between the epoxy groups and the amino groups of now had a pencil hardness approaching 4H, at which hardness the
the PEI. The net result is a surface replete with amino groups that coating exhibited some damage and delamination.
are covalently anchored onto the surface. Multilayers of CHI/ To mimic the pencil hardness test and better explore the
CMC were then assembled onto this surface starting with CMC. mechanical durability of the films on glass substrates, AFM
In the latter case, the CHI/CMC multilayers were cross-linked was utilized to apply scratches to the films in certain directions
postassembly with EDC/NHS chemistry, followed by reaction using the nanolithography mode at different forces. The CHI/
with glutaraldehyde. CMC films, including films with 12.5, 14.5, 16.5, and 30.5
Following this procedure, it was found that the cross-linked bilayers, with and without cross-linking were evaluated. The as-
multilayer films exhibited superhydrophilic wetting behavior and assembled films were readily damaged, even with a 400 nN force
retained their good antifog performance. The change from (Figure S.2); however, the cross-linked films showed no damage
hydrophilic to superhydrophilic wetting behavior after cross- even with a 3000 nN force (Figure S.2). Therefore, these results
linking suggested that significant morphological changes had were consistent with pencil and sponge-cloth rubbing test results.
been introduced by this chemistry. AFM and SEM images of From a sectional analysis of the non-cross-linked (CMC/CHI)14.5
the cross-linked and as-assembled CHI/CMC films (Figure 12) coatings, it can be seen that the depth of scratched areas of the film
revealed that surface roughness increased from 6 to 25 nm and was 23 nm at 1.5 μN and 12 nm at 1 μN. Because of the roughness
of the (CMC/CHI)14.5 films after cross-linking, it was difficult to
(28) Tsai, T.-Y.; Wen, C.-K.; Chuang, H.-J.; Lin, M.-J.; Ray, U. Polym. judge the exact depth of the scratch. On the basis of the average
Compos. 2008, 30, 1552–1561. results, it seems that the depth of the scratch was around 20 nm.

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Nuraje et al. Article

In order to further explore the mechanical enhancement of the water droplets observed in the fogging films. The long-lasting
cross-linked system, the adhesion of the multilayer film on glass antifog properties of these coatings open up new possibilities for
substrates before and after cross-linking was evaluated via a biomedical and optical devices that require easily applied and
crosshatch adhesion test (Scotch tape test). As-assembled films durable antifog coatings.
failed the Scotch tape test, whereas cross-linked films remained
intact after the test. Thus, chemically anchoring the multilayer to Acknowledgment. This work was supported partially by the
the glass surface dramatically improved adhesion. MRSEC Program of the National Science Foundation (DMR-
0819762 and DMR-0213282). The authors thank the Center for
4. Conclusions Materials Science and Engineering (CMSE) and the Institute for
Soldier Nanotechnologies (ISN) for use of the characterization
This work demonstrates that layer-by-layer assembled thin facilities. We also acknowledge the contribution of Dr. Junyoung
films rich in polysaccharides can exhibit excellent antifog proper- Kim and Mr. Girma Endale for helpful discussions and some
ties under a variety of environmental challenges. With suitable sample characterizations. The authors also thank Dr. Haipeng
surface and cross-linking chemistry, thin-film coatings with very Zheng of Essilor company for valuable input discussions.
good mechanical durability and adhesion can be realized. ESEM
studies provided direct evidence that the excellent antifog capabil- Supporting Information Available: ESEM movies, optical
ities of the polysaccharide-containing multilayers were associated images, and AFM images. This material is available free of
with the formation of water sheets as opposed to light-scattering charge via the Internet at http://pubs.acs.org.

Langmuir 2011, 27(2), 782–791 DOI: 10.1021/la103754a 791