Justin A.
Kleingartner‡
a,
Hyomin
Lee‡
a,
Michael F.
Rubner
*b,
Gareth H.
McKinley
*c and
Robert E.
Cohen
*a
aDepartment of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA. E-mail: recohen@mit.edu; Tel: +1 617 253 3777
bDepartment of Material Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA. E-mail: rubner@mit.edu; Tel: +1 617 253 0094
cDepartment of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA. E-mail: gareth@mit.edu; Tel: +1 617 258 0754
First published on 20th May 2013
Switchable polymer multilayer coatings consisting of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) were prepared via Layer-by-Layer (LbL) assembly and post-functionalized with poly(ethylene glycol methyl ether) (PEG). This resulted in a soft polar coating that reversibly and repeatedly rearranges from hydrophobic to hydrophilic (or vice versa) when contacted with water (or air). Goniometry is used to quantify the forward surface rearrangement in the form of transient measurements of the water contact angle. By examining the time evolution of the water contact angle at various temperatures, the apparent activation energy for the forward surface rearrangement (Ea,f) can be determined. Further insight can be gained into the kinetics of this surface reconstruction process by utilizing dynamic tensiometry to measure the evolution in the contact angle of a liquid meniscus at several rates and temperatures as it advances or recedes over the multilayer films. A simple first-order thermally-activated rate process is shown to describe the forward and reverse surface reconstruction and enables the shape of the measured tensiometric force curves during repeated immersion and emersion to be predicted quantitatively. Using this model we show that the character of this switchable surface coating can appear to be hydrophobic or hydrophilic depending on a single dimensionless parameter which incorporates the characteristic time-scale for temperature-dependent surface rearrangement, the speed of immersion and the capillary length of the liquid meniscus.
Previous work has primarily focused on measuring contact angle hysteresis (CAH = θadv − θrec) to quantify surface reconstruction phenomena.7,20 Although large contact angle hysteresis has been associated with significant surface reconstruction,7,8 surface roughness21 and chemical heterogeneity22,23 also result in hysteresis even in the absence of surface reconstruction. A more insightful characterization of surface reconstruction can be accomplished through quantitative investigation into the kinetics of surface rearrangement. Recently, time dependent measurements of contact angles on various reconfigurable surfaces have been used to probe the rate of the surface rearrangement of biopolymer coatings,2 poly(methyl methacrylate) (PMMA),5 and siloxane-based polymeric surfaces.4
Morra et al. have previously used dynamic tensiometry to investigate rearranging hydrogel surfaces.13 In the present work, we show that rate and temperature dependent tensiometry measurements provide a powerful framework for completely characterizing the forward (hydrophobic to hydrophilic) and reverse (hydrophilic to hydrophobic) reconstruction phenomena, as well as the temperature dependencies of these thermally-activated kinetic processes. In a dynamic tensiometer, force and relative position data are collected while a container of probe liquid is raised and lowered at a constant velocity such that the liquid contact line advances (or recedes) across the solid surface at a programmed speed. In the quasi-static limit, when viscous forces are negligible, the net force acting on the sample results from a combination of interfacial and buoyant forces and is given by F = Pγlvcos θ − ρlgAx, where P is the total perimeter of the solid–liquid–air contact line, γlv is the probe liquid surface tension, ρl is the liquid density, g is the gravitational acceleration, A is the cross-sectional area of the immersed solid, and x is the immersed depth of the solid.24,25 This force balance can be conveniently nondimensionalized, scaling the resultant tensiometric force by Pγlv (the maximum possible interfacial force in the vertical direction) and the immersed depth by (the maximum height associated with capillary rise of a liquid meniscus on the solid in the limit of perfect wetting θ → 0), where
.26 This scaling allows for a more insightful analysis of the shape of tensiometric force traces and results in the compact expression
![]() ![]() | (1) |
In the search for a mechanically robust antifrost, and antifogging coating, we have recently developed a new multilayer system.27 This system exhibited two interesting characteristics: One is zwitter-wettable behavior whereby the multilayer film exhibits a facile, rapid absorption of water into a film from the gas phase while simultaneously exhibiting very high contact angles for drops of liquid water placed on the surface of the same film, and the other is transient water contact angle behavior. The former feature has been discussed in detail previously.27 In the present study, we investigate the time-dependent wetting behavior of these coatings, which results from the transient surface rearrangement of hydrophilic functional groups towards the surface in response to exposure to a liquid water environment.
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Fig. 1 Procedure for the fabrication of PEG-functionalized PVA/PAA multilayer film on glass substrate. |
The dynamics of this molecular-scale, surface rearrangement were first investigated through the measurement of changes in the surface wetting properties of the coatings. Goniometric measurements of the time-dependent contact angle with water were conducted for PEG-functionalized PVA/PAA multilayer films and fluorosilane-treated glass slides as shown in Fig. 2a. The surfaces of all of these coatings exhibited initial advancing water contact angles greater than 100°. In the case of the fluorosilane-treated glass (initial advancing contact angle of 112 ± 1°), the water contact angle decreased by less than 10° over the period of 20 min, which can be attributed to evaporation of fluid from the static drop over the elapsed time of the experiment. For the PEG-functionalized PVA/PAA multilayer film, the initial water contact angle (θi = 117 ± 1°) decreased monotonically dropping to approximately 40° after 20 min. After the initial stage of rapid decay, the water contact angle decreased linearly with time in a similar fashion to the fluorosilane-treated glass slide. The linear decrease in contact angle at long times is expected as a result of evaporation and has been reported by others.2,5
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Fig. 2 (a) Time dependence of water contact angles θ for the PEG-functionalized PVA/PAA multilayer film and fluorosilane-treated glass at room temperature (22 ± 1 °C). Open boxes, and circles represent individual data points averaged every 10 s while the bold line represents the model fit; (b) changes in advancing water contact angles θadv by alternating between dry and hydrated conditions for PEG-functionalized PVA/PAA multilayer film. |
The PEG-functionalized PVA/PAA multilayer films possess two particularly striking features: they have an unusually high initial water contact angle for a coating that is produced entirely from water-soluble polymers, as well as a very strong transient water contact angle behavior (exhibiting a large decay in contact angle upon exposure to a liquid water drop). The former feature has been discussed in detail previously27 and results from the combined effects of an initial surface enrichment of hydrophobic acetate moieties and the softness of the multilayer film. The latter feature can be rationalized in the context of surface reconstruction, specifically the time-dependent spatial orientation of hydrophobic and hydrophilic functional groups at the liquid water–solid polymer interface.1,2,4–6,11 To test the latter hypothesis, contact angle measurements were performed on the same samples using two nonpolar liquids, diiodomethane (DM) and hexadecane (HD), with surface tension values of γDMlv = 50.8 mN m−1 and γHDlv = 27.5 mN m−1, respectively. These results are shown in the ESI (Fig. S1†). Both liquids exhibited low contact angle hysteresis (CAH ≈ 15°) on the LbL films and only a weak linear time dependence in their contact angles, which can again be attributed to evaporation. There was no evidence of the strong exponential transient response in the contact angle measured with liquid droplets of DM or HD. This suggests that the hydrophilic groups buried just beneath the surface of the initially-dry films are not driven to the solid–liquid interface when nonpolar liquids are used to probe the surface.
The reversibility of the surface reconstruction, shown in Fig. 2b, was investigated by measuring the initial advancing water contact angle while alternating the environment between hydrated and dry states. The PEG-functionalized PVA/PAA multilayer film, which exhibits an initially hydrophobic contact angle, was repeatedly placed in hydrated conditions (submerged in water) and then dried in ambient lab conditions (22 ± 1 °C, 40 ± 10% RH) for 15 min.10 In the hydrated state the film exhibited an advancing water contact angle near zero, which is likely due to a thin residual layer of adsorbed water covering the surface. As the surface is gradually dried under ambient conditions, the initial advancing water contact angle increased from 0° to more than 100° indicating that the surface of the multilayer film reconfigures as water molecules are removed to enrich the concentration of lower energy hydrophobic acetate moieties to the hydrophobic state. After five cycles the film still displayed complete reversibility (Fig. 2b).
The initial rapid response of the surface reconfiguration can be characterized by an exponential of the form ∼exp(−t/τf) where τf is a material-dependent time constant. Furthermore, if this surface reconstruction is viewed as a thermally-activated process, the characteristic time scale (τf) of the mechanism should depend on temperature according to an Arrhenius or similar formalism. This aspect of the film behavior was explored goniometrically by performing time dependent measurements of the water contact angle at T = 10, 20, 30, and 40 °C. The results of these experiments are shown in Fig. 3a. The initial exponential decay of the water contact angle clearly proceeds more rapidly at higher temperatures. The forward surface rearrangement occurs within the first half of the experiment and the subsequent linear decrease in the measured contact angle was used to estimate the evaporation rate. The time constant for the forward surface rearrangement (τf) was then determined after removing the effects of evaporation. The surface rearrangement was modeled as a first-order process:
![]() | (2) |
![]() | ||
Fig. 3 (a) Time dependence of the water contact angle θ for the PEG-functionalized PVA/PAA multilayer film at T = 10, 20, 30, 40 °C. The individual data points represent the average value of three separate measurements over 10 s intervals; (b) a plot of ln τfversus T−1 where τf is obtained from fits of the transient data in (a) after correcting for evaporation. |
Table 1 shows clearly that the time constant characterizing surface reconstruction in the PEG-functionalized PVA/PAA multilayer films decreases with increasing temperature, while θphob and θphil remain nearly constant. The temperature dependence of the surface rearrangement rate was assumed to follow an Arrhenius form:
τf−1 = Afexp(−Ea,f/RT) | (3) |
Temperature (°C) | θ phob (deg) | θ phil (deg) | τ f (s) |
---|---|---|---|
10 | 110 ± 3 | 69 ± 13 | 79 ± 19 |
20 | 111 ± 8 | 67 ± 8 | 54 ± 18 |
30 | 110 ± 7 | 60 ± 14 | 34 ± 5 |
40 | 105 ± 16 | 66 ± 12 | 14 ± 1 |
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Fig. 4 (a) Schematic of the PEG-functionalized PVA/PAA multilayer film undergoing surface reconstruction during the first tensiometric immersion in water. Hydrophobic moieties are represented by acetate groups and hydrophilic groups, such as PEG and carboxylic acid groups, are represented by hydroxyl groups; (b) force trace for the first immersion of the PEG-functionalized PVA/PAA multilayer film into water at 30 °C occurring at three different rates. Solid red (![]() ![]() ![]() |
The extent of surface rearrangement in the PEG-functionalized PVA/PAA multilayer film is manifest in the advancing water contact angle of the surface. In a goniometric system the time evolution of the advancing water contact angle on the surface is observed; in the case of tensiometry, a single velocity-dependent advancing water contact angle is observed where the deflection of the liquid meniscus (i.e., the contact angle) reaches a steady state configuration as the three-phase contact line advances across the surface. If the selected rate of immersion, V, is much faster than the rearrangement kinetics, then the high advancing water contact angle associated with the initial hydrophobic state is expected to dominate the tensiometric measurements. Conversely, very slow immersion will produce tensiometric data that approach the asymptotic hydrophilic behavior that was observed in goniometric experiments at long times.
To quantify the qualitative descriptions of “slow” and “fast,” first observed by Morra et al.,13 we compare the time scale associated with molecular rearrangement τf with the characteristic time scale at which the liquid meniscus advances across the surface during the immersion process τc = cap/V, where
cap is the capillary length of the liquid. The resulting dimensionless ratio of time scales for the forward rearrangement is given by
![]() | (4) |
In the limit αf ≪ 1 we expect surface rearrangement to be fast so that the advancing contact angle is small and the surface appears hydrophilic. If αf ≫ 1 the meniscus advances very rapidly compared to the rearrangement rate and the surface will appear hydrophobic. Eqn (2) models the advancing contact angle of the reconfiguring surface as a function of elapsed rearrangement time. If we evaluate this equation after a characteristic elapsed time of tc = cap/V we obtain the following expression:
![]() | (5) |
A transition from a high contact angle regime (θ ≈ θphob) to a rearrangement-dominated, low contact angle regime (θ ≈ θphil) is expected as the magnitude of the dimensionless group αf passes through unity.
Similarly, the reverse rearrangement can also be modeled as a first-order thermally-activated rate process with the additional consideration of the evaporation of bulk water from the surface of the previously immersed and swollen multilayer film. For simplicity, we assume that the reverse rearrangement does not begin until the excess water evaporates from the surface of the film (i.e., after a delay time td). Therefore, the following first-order model with time delay is used to describe the reverse surface rearrangement:
![]() | (6) |
In addition to varying the rate of immersion/emersion, V/cap, the temperature of the fluid was also varied in the tensiometry experiments to further characterize the kinetics of the surface rearrangement phenomena. Experiments were carried out at four temperatures (40 °C, 30 °C, 20 °C, and 10 °C) and three speeds (1.0 mm s−1, 0.1 mm s−1, and 0.01 mm s−1). The force traces for the first immersion at 10 °C at the three experimental speeds are shown in Fig. 4c. Unlike the results seen in the 30 °C data of Fig. 4b, at 10 °C the results of the three experiments nearly coincide and the advancing contact angle of 120 ± 7° that is extracted from the data is close to the initial hydrophobic state value of 111 ± 4° obtained via goniometry. Thus at 10 °C the rate of the forward rearrangement is significantly slower than the rate of contact line advancement (i.e., αf > 1), even at the lowest experimental velocity of 10−2 mm s−1.
The full set of rate- and temperature-dependent immersion and emersion tensiometry data is shown in Fig. 5. As expected, upon immersing at the highest speed (right most column of plots in Fig. 5) the initial advancement into water yields a high initial contact angle (F0 < 0) throughout the first immersion. After exposure to water, the contact line recedes with a low receding contact angle (F0 > 0) over the rearranged surface. Subsequent immersion/emersion cycles show only the low contact angle, rearrangement-dominated regime, because the surface does not have time to revert back to the hydrophobic state at the high immersion/emersion speed (i.e., the analogous dimensionless parameter for the reverse surface rearrangement is αr ≫ 1). Experiments carried out at a speed that is an order of magnitude lower (middle column of plots in Fig. 5) show that the initial advancement of the meniscus still proceeds with a high advancing contact angle and after exposure to water the contact line recedes with a low receding contact angle. However, upon a second advancement into water, the advancing contact angle exhibits transient behavior as the surface rearranges back to its initial hydrophobic state. At this instrument speed the sample is exposed to air for a sufficient period of time that the reverse surface rearrangement (from the hydrophilic to the hydrophobic state) occurs within the time scale of the experiment (i.e., αr ∼ 1). This behavior is repeated in subsequent cycles, which highlights the complete reversibility of this surface switching phenomena. Finally, immersing at the slowest speed (V = 0.01 mm s−1), the advancing force traces indicate that the surface is hydrophilic (F0 > 0) for temperatures T ≥ 20 °C. The rate of surface reconfiguration is fast (αf < 1) compared to the translation rate of the meniscus. Subsequent immersions again show recovery towards θ → θα,f introduced in eqn (6) since the surface has sufficient time out of the water to undergo the reverse rearrangement.
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Fig. 5 Dynamic tensiometry measurements for switchable PEG-functionalized PVA/PAA multilayer films probed with water. Three rates and four water temperatures were examined. Solid red (![]() ![]() ![]() |
The effect of temperature on the surface rearrangement can be clearly seen in the lowest immersion/emersion speed (0.01 mm s−1) data taken at 10 °C and 20 °C. At 20 °C the surface appears hydrophilic even during the first immersion with a low contact angle and positive force intercept, F0; however, at 10 °C the surface rearrangement has slowed enough (τ10 °Cf > τ20 °Cf) that the initial immersion now occurs faster than the time scale of rearrangement (i.e., αf > 1) and the surface appears hydrophobic with a high advancing contact angle. Likewise, the effect of temperature on the reverse rearrangement (from the hydrophilic to the hydrophobic regime) can be observed in the intermediate rate (0.1 mm s−1) results. The recovery to the hydrophobic state (observed during the second immersion) occurs more rapidly at 40 °C than at 10 °C. The higher temperature increases the rate of surface rearrangement and allows for faster restoration of the hydrophobic state.
Variable | Units | Goniometry | Tensiometry |
---|---|---|---|
a Values are averaged from the contact angles obtained for different temperatures (Table 1). b t d, log10Ar, and Ea,r are not available because goniometry can only probe the forward surface rearrangement. | |||
θ phob | degrees | 109a | 125 |
θ phil | degrees | 66a | 53 |
log10Af | — | 5.5 | 4.7 |
E a,f | kJ mol−1 | 40.5 | 40.1 |
θ rec | degrees | 16 | 25 |
t d | seconds | —b | 151 |
log10Ar | — | —b | 1.2 |
E a,r | kJ mol−1 | —b | 18.5 |
Table 2 shows that good agreement between the Arrhenius parameters can be obtained from the two experimental methods (goniometry and tensiometry) for the forward surface rearrangement. The activation energy of this process arises from the segmental motion of hydrophobic and hydrophilic moieties at the interface between the PEG-functionalized PVA/PAA multilayer film and liquid water.
The value for the advancing water contact angle in the hydrophobic regime (θphob) obtained from tensiometry is slightly higher than the value obtained from goniometry, which is due to the inherent experimental difficulties in obtaining this value with a goniometer. The surface immediately begins to rearrange when contacted with water and as a result several seconds elapse between placing the drop, the decay of all internal motion, and starting the contact angle measurement in a goniometric system. Tensiometry avoids this issue by immersing the sample into a reservoir of the probe liquid at a slow fixed speed and the tensile force on the surface is measured in real time. The advancing water contact angle is then obtained from regression of eqn (1) to the linear portion of the immersion force traces.
The force traces produced from the dynamic model with the fitted parameters from Table 2 are shown with the corresponding experimental data in Fig. 6 and 7 for selected temperatures and rates. The complete set of model results plotted in a form analogous to Fig. 5 can be found in the ESI (Fig. S4†) with their corresponding αf values.
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Fig. 6 Comparison of the predicted values and measurements for the tensiometric force of PEG-functionalized PVA/PAA multilayer films probed with water at 0.01 mm s−1 during immersion and emersion. Solid red (![]() ![]() ![]() |
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Fig. 7 Comparison of the predicted values and measurements for the tensiometric force of PEG-functionalized PVA/PAA multilayer films probed with water at 20 °C. Solid red (![]() ![]() ![]() |
In general, good agreement is observed between the model and the data. In Fig. 6 the initial advancing contact angle is in agreement with the data, and the fitted activation energy of 40.1 kJ mol−1 captures the temperature dependence of the rearrangement process. The effect of immersion speed is clearly illustrated by Fig. 7. At low wetting speeds (αf ≲ O(1)) the surface rearranges as it is exposed to water and the surface appears hydrophilic (i.e., F0 > 0). However, at high immersion speeds (αf ≫ 1) the surface appears strongly hydrophobic. The onset and duration of the reverse rearrangement is also well predicted by the model for both varying rate and temperature; however, the shape of the force trace during the reverse rearrangement associated with the second and third immersion cycles does not fully agree with the experimental data. The small deviations are most likely a result of some surface rearrangement taking place as the excess water dries from the exposed sample surface, which the model does not account for. The parameter values for the model characterizing the reverse rearrangement are also expected to be less accurate than the corresponding forward rearrangement parameters, because the air temperature and humidity (i.e., the ambient environment in which the reverse rearrangement occurred) was not rigorously controlled. As a result, the surface temperature of the multilayer film during the reverse rearrangement is not necessarily the same as the temperature of the probe liquid. IR thermal imaging of the films during the tensiometer experiment (Fig. S5 in the ESI†), show that at low temperatures (10 °C) the multilayer film is at the liquid temperature during the reverse rearrangement; however, at higher temperatures (40 °C) the multilayer film rapidly cools as a result of evaporation of the water during rearrangement with most of the process occurring at ambient temperatures (∼22 °C).
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c3sm50596k |
‡ These authors contributed equally. |
This journal is © The Royal Society of Chemistry 2013 |