Article pubs.acs.org/Langmuir
Versatile Approach for the Fabrication of Functional Wrinkled Polymer Surfaces Marta Palacios-Cuesta,† Marta Liras,†,§ Adolfo del Campo,‡ Olga García,*,† and Juan Rodríguez-Hernández*,† †
Department of Chemistry and Properties of Polymers, Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, Spain ‡ Instituto de Cerámica y Vidrio (ICV-CSIC), Kelsen 5, 28049 Madrid, Spain ABSTRACT: A simple and versatile approach to obtaining patterned surfaces via wrinkle formation with variable dimensions and functionality is described. The method consists of the simultaneous heating and irradiation with UV light of a photosensitive monomer solution confined between two substrates with variable spacer thicknesses. Under these conditions, the system is photo-crosslinked, producing a rapid volume contraction while capillary forces attempt to maintain the contact between the monomer mixture and the cover. As a result of these two interacting forces, surface wrinkles were formed. Several parameters play a key role in the formation and final characteristics (amplitude and period) of the wrinkles generated, including the formulation of the photosensitive solution (e.g., the composition of the monomer mixture) and preparation conditions (e.g., temperature employed, irradiation time, and film thickness). Finally, in addition, the possibility of modifying the surface chemical composition of these wrinkled surfaces was investigated. For this purpose, either hydrophilic or hydrophobic comonomers were included in the photosensitive mixture. The resulting surface chemical composition could be finely tuned as was demonstrated by significant variations in the wettability of the structured surfaces, between 56° and 104°, when hydrophilic and hydrophobic monomers were incorporated, respectively
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INTRODUCTION Surface instabilities have received particular attention because they can be employed to pattern polymer surfaces and generate a variety of nano- and microstructures. Surface instabilities produced in polymer films that have led to patterned surfaces include dewetting in thin films,1−8 phase separation of polymer blends or block copolymers, 9−11 the use of modified substrates,6,12,13 electric fields,14−18 or formation of surface wrinkles.19−23 While initially both buckling and wrinkling were considered as undesirable mechanical instabilities, our understanding of the mechanism of formation and the large amount of potential applications has stimulated interest in this particular approach to pattern polymer surfaces.24−27 As examples, wrinkled surfaces have been employed to prepare electrodes for electroactive28/conductive29 polymer actuators and anticorrosive coatings,30 to produce high-performance electronics on rubber substrates,31 and to produce surfaces with controlled wettability, for instance, with superhydrophilic22 or anisotropic wetting behavior on tunable surfaces.20 More recently, in combination with surface-nanopatterned substrates, anisotropic and hierarchically structured interfaces were obtained by Stafford and co-workers.27 Although the formation of wrinkles on a polymer surface has been achieved by different approaches,32−37 in general the fabrication of this particular type of surface pattern is accomplished using a soft material with low elastic moduli, © XXXX American Chemical Society
typically PDMS, as a substrate. During either mechanical stretching/compression or thermal expansion, a rigid layer (a metal,38,39 a polymer layer,28 or simple oxidation of the PDMS substrate40,41) is deposited on top of the material. Relaxation of the forces applied,42 heating,43 or cooling to room temperature38,44 induces, upon buckling, the formation of surface wrinkles. The first method reported used the evaporation of aluminum on a flexible substrate to form a rigid layer.38 The metal was spread on the thermally expanded PDMS layer (high temperature) that, upon cooling, contracts and induces the formation of wrinkles in the metallic layer. Other methods for obtaining a rigid layer involve the oxidation of the PDMS film with UV−ozone and plasma treatment.40,41 Depending on the conditions employed and the oxidative method, microstructures with surface wrinkles from 150 nm to several hundreds of micrometers can be obtained. However, the different mechanical resistance of the layer deposited compared to the bulk limits the lifetime of the wrinkles and may induce cracking on the surface formed. Moreover, the chemical composition is limited to selected metals, oxides resulting from surface treatments, or coatings with high-modulus polymers. Received: May 13, 2014 Revised: October 13, 2014
A
dx.doi.org/10.1021/la502913w | Langmuir XXXX, XXX, XXX−XXX
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fluorostyrene (5FS)] was included at variable ratios to produce functional wrinkles with variable dimensions with the aim of simultaneously controlling the chemical composition. This allowed buckled surfaces with a variable chemical composition to be generated depending on the initial monomer composition.
As an alternative to the aforementioned examples, recently several groups have described the formation of wrinkled interfaces, replacing the PDMS substrate with other polymeric coatings such as hydrogels or photo-cross-linkable systems.45,46 On one hand, confinement of hydrogels has been demonstrated to induce surface deformations that may lead to surface instabilities and finally to wrinkle formation.35,47−50 In these homogeneously cross-linked materials, the presence of a rigid support is responsible for the surface deformation. On the other hand, photo-cross-linkable systems are based on a vertical gradient in the cross-linking degree from the air−polymer interface to the polymer−support interface. Upon surface deformation, for instance, by swelling, the interface buckles and forms wrinkles. One of the most recently described approaches to forming wrinkled surfaces employs irradiation in two steps of an acrylate mixture.51 To create microstructures, the sample is irradiated with a monochromatic excimer lamp with a small penetration depth that polymerizes only the top layer of the photosensitive mixture. This gradually photopolymerized layer floats on the nonpolymerized mixture, and because of the volume contraction superficial wrinkles are formed. In a second step designed to fix the structure, the system is treated using through-curing irradiation with, for instance, a Hg lamp. As an illustrative example, Crosby et al.50 employed a mixture formed by acrylic monomers and a cross-linker and irradiated the mixture while applying a controlled oxygen flow on top of the sample. As mentioned above, wrinkles prepared, for instance, using a PDMS substrate allow fine-tuning of the wrinkle characteristics. However, variations in the chemical composition required the deposition of a functional layer. Equally, the microfolded surfaces obtained from hydrogels or photo-cross-linked materials have been employed using particular systems52 of acrylic monomers.50 These were conducted in two steps, and the wrinkle dimensions seem to be difficult to control. In addition, the pattern completely changes with a change in the formulation51 or is limited to a particular system,53 wrinkle formation requires a large amount of non-cross-linked monomer, and the unreacted monomer partially remains in the polymer film and needs to be removed to prevent further side reactions. In this work, we describe the elaboration of wrinkled surfaces with significant advantages over previous approaches52,54 based on the confinement of monomer mixtures between two interfaces varying the distance between them with a spacer. First, by using simultaneous photo-cross-linking and heating, functional wrinkled interfaces with variable buckle dimensions (amplitude and period) depending on the monomer/crosslinking agent ratio and the spacer employed were prepared in a single straightforward step. In addition, in this case, the reactive conversion is complete so that the presence of residual monomer, present in previously reported approaches, is avoided. Finally, monomer confinement between support and cover allowed the use of low-boiling point monomers that would evaporate if other approaches were employed. The mixture of a difunctional monomer [ethylene glycol dimethacrylate (EGDMA) for the acrylates and divinylbenzene (DVB) for styrenics] with a linear monomer [methyl methacrylate (MMA) or styrene (S)] was employed. First, we will describe the role of the temperature and thickness in wrinkle formation. Subsequently, functional acrylates [2hydroxyethyl methacrylate (HEMA) and trifluoroethyl methacrylate (TFMA)] or a styrene derivative monomer [penta-
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EXPERIMENTAL SECTION
Materials and Methods. Methyl methacrylate (MMA) was washed three times with a basic aqueous solution (10% NaOH) and three additional times with water. Then, the resulting monomer was dried on anhydrous magnesium sulfate, filtered, and distilled. Styrene (S) was dried under CaH2 and distilled under reduced pressure. Ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB), 2(hydroxyethyl methacrylate) (HEMA), 2,2,2-trifluoroethyl methacrylate (TFMA), and 2,3,4,5,6-pentafluorostyrene (5FS) (all from Aldrich with the highest purity); Irgacure 651 (IRG 651) and 2,2-dimethoxy1,2-diphenylethan-1-one (Ciba); and dichlorodimethylsilane (Aldrich, 98.5%) and the rest of the solvents were employed as received without further purification. Silicon wafers (Siegert Consulting e.k.) and 0.15 mm thickness glass covers (Menzel-Glaser) were employed as supports. Infrared spectra were recorded using a Spectrum One FTIR spectrometer (PerkinElmer) fitted with a horizontal attenuated total reflectance (ATR) accessory under unforced conditions. The irradiated samples were placed in direct contact with the diamond crystal with no previous preparation. Spectra were collected at 8 cm−1 resolution by co-adding six scans per spectrum. Scanning electron microscopy (SEM) was used for surface structural and cross-sectional analysis. Micrographs were taken using a Philips XL30 instrument with an acceleration voltage of 25 kV. The samples were coated with gold and palladium (80/20) prior to scanning. Cross sectional profiles and three-dimensional (3D) images of the wrinkled surfaces were characterized by using a Zeta-20 True Color 3D Optical Profiler from Zeta Instruments. Methodology for Preparing the Wrinkles. Photosensitive mixtures contained variable amounts of a cross-linking agent, i.e., ethylene glycol dimethacrylate (EGDMA) for the methacrylic monomers and divinylbenzene (DVB) for the styrenics and the corresponding linear monomers. The methacrylic linear monomers employed throughout this study were methyl methacrylate (MMA), 2hydroxyethyl methacrylate (HEMA), and 2,2,2-trifluoroethyl methacrylate (TFMA) in different ratios and were copolymerized with EGDMA. The styrenic monomers employed were styrene (S) and 2,3,4,5,6-pentafluorostyrene (5FS) and were copolymerized with DVB. In addition, a radical photoinitiator, IRG 651 (2 wt % with respect to the total amount of monomers), was employed to start the polymerization process. The photopolymerization of the films was undertaken under a UV spotlight irradiation source using a Hamamatsu model Lightning Cure L8868 instrument provided by a 200 W Hg−Xe lamp. To prepare the films, 2 cm × 2 cm silicon wafers with variable spacers (50−150 μm) were employed. A few drops of the photosensitive mixture were placed in the center of the wafer and covered with 0.30 mm thick glass. The samples were preheated on a hot plate and irradiated under constant heating. The incident light was focused on the samples with an optical fiber (sample−light distance fixed at 8 cm), and the irradiation intensity was kept constant at 6150 mW/m2 (measured by a Luzchem SPR-01 radiometer) throughout the experiments. Initial tests were conducted by varying the ratio of linear monomer versus cross-linking agent to optimize wrinkle formation. The samples having additionally functional monomers were prepared using a constant ratio of linear monomers (i.e., both functional monomer and nonfunctional monomer) and cross-linking agent of 85/15 (v/v).
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RESULTS AND DISCUSSION Mechanism of Wrinkle Formation. Wrinkled topographies were prepared using the setup described in Scheme
B
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Scheme 1. (A) Illustration of the Experimental Procedure Used To Fabricate Wrinkled Surfaces for MMA/EGDMA/IRG Mixturesa and (B) a 3D Image Obtained by Using an Optical 3D Optical Profiler That Corresponds to a Photosensitive Mixture (C) Containing 85% (v/v) Monomer (MMA), 15% (v/v) Cross-Linking Agent (EGDMA), and 2 wt % Photoinitiator (IRG 651)
a
The sample is irradiated and heated. During this process, volume contraction and capillary forces act simultaneously inducing the formation of wrinkled interfaces.
Scheme 2. Chemical Structures of the Monomers, Cross-Linking Agents, and the Photoinitiator Employed in This Studya
a
We explored two different families of monomer/cross-linking agent mixtures: (A) methyl methacrylate/EGDMA and (A′) styrene/DVB. Additionally, monomers MMA and S in the mixture have been partially or completely substituted with other functional monomers (B and B′, respectively) to vary the chemical composition of the wrinkled interface.
1. The monofunctional monomer (MMA) was mixed with the cross-linking agent [ethylene glycol dimethacrylate (EGDMA)] and the photoinitiator (IRG 651), and the mixture was confined in a closed chamber. The liquid mixture was then simultaneously heated and irradiated using UV light that could pass through the glass cover employed. After irradiation for 4
min, the reaction was completed and the cover removed. The use of a cover avoids monomer evaporation, thus assuring that the composition of the final material is identical to the feed composition. Moreover, a planar cover limits variations in thickness over the sample and favors the homogeneity of the surface pattern. As a result of the simultaneous irradiation and C
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Figure 1. (A) Optical micrographs of the surface patterns formed by photo-cross-linking of the MMA/EGDMA mixture [85/15 (v/v)] and 2 wt % IRG 651 at different temperatures (50, 70, 90, and 100 °C). The monomer mixture was allowed to reach the desired temperature prior to irradiation. The scale bar is 500 μm. (B) FTIR-ATR spectra (left) of the cross-linked films obtained by simultaneous heating and UV irradiation of the MMA/ EGDMA monomer mixture [85/15 (v/v)] at different temperatures. Representation of the Band I/Band II ratio (right) as a function of the photocross-linking temperature employed.
different families of monomers, i.e., acrylics and styrenics, that may provide materials with different surface wettabilities, for example. In the EGDMA/MMA mixture, the MMA was partially or totally substituted with a functional monomer: either hydrophilic (HEMA) or hydrophobic (TFMA). Equally for the DVB/S mixture, the linear monomer, i.e., styrene, was
photo-cross-linking, wrinkled structures such as the example shown in Scheme 1B were observed. The approach illustrated in Scheme 1 has been extended to other monomers to demonstrate the versatility of this strategy. More precisely, Scheme 2 shows the chemical structures of monomers, cross-linking agents, and the photoinitiator employed throughout this study. We have explored two D
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Figure 2. Optical micrographs of the formation of wrinkles at different polymerization stages: (A) initial monomer mixture, (B) formation of nucleation points, (C) extension of the nucleation, and (D) final formation of wrinkles.
double bonds of the acrylic functionality (−CHCH− twisting). At low temperatures, a relatively large amount of residual double bonds is present in the film upon photopolymerization. Nevertheless, with an increase in temperature the intensity of the −CC− signal decreases while the −C− C− band observed at ∼840 cm−1 is relatively more intense. We can thus conclude that increasing the temperature increases the level of effective cross-linking. The amount of residual −C C− is reduced, producing an increase of the volume contraction upon UV irradiation. In addition, Figure 1B exhibits the ratio of Band I and Band II as a function of the photo-cross-linking temperature employed. This explains, at least to some extent, not only the formation of wrinkled interfaces but also why surface wrinkles were produced to a larger extent when the reaction was conducted at higher temperatures. According to the optical profiler images depicted in Figure 2, obtained at different reaction stages, wrinkle formation may occur as follows. The initial monomer mixture fills the volume between the covers. When the photopolymerization starts, as a consequence of volume contraction, cavities with rather irregular dimensions are formed (Figure 2B). The polymerization continues, and as a consequence of volume contraction, an enlargement of the cavities is observed (Figure 2C). As a result of this process, the cavities interconnect before the completion of the reaction and produce a completely wrinkled film. According to these experimental observations, we can hypothesize that wrinkle formation might be the result of interplay between two different forces acting simultaneously. In Scheme 3 are depicted the 3D images of a wrinkled surface (A) and a cross section of a particular wrinkle (B). The characteristic wrinkle profile also confirmed the presence of
partially or totally replaced with HEMA (hydrophilic) or 5FS (hydrophobic). However, before the variations in surface functionality were explored, the experimental conditions for performing the photopolymerizations were optimized. Initially, the photopolymerization reactions were undertaken at different temperatures, and the surface patterns were observed to change dramatically as a function of the temperature employed. The samples were irradiated with UV light while heating was maintained for 4 min. The micrometer size surface features formed using MMA [85% (v/v)] and EGDMA [15% (v/v)] using 2 wt % IRG 651 as a photoinitiator are depicted in Figure 1A. Whereas for temperatures from room temperature to 70 °C no significant, or only partial, wrinkle formation was observed, at 100 °C the formation of micrometer-sized wrinkles was quite homogeneous over the entire film. It should be mentioned that in the case of styrene/DVB mixtures the temperature required to observe the formation of wrinkled interfaces was 140 °C. Indeed, the photopolymerization kinetics of the S/DVB mixture was slow in comparison to that of the MMA/ EGDMA mixture, and additional heating was required. It should be mentioned at this point that the monomer conversion achieved is almost complete. Analysis conducted by washing the films with organic solvents to extract residual monomer and further analysis by nuclear magnetic resonance confirmed the complete consumption of the monomers in the photo-cross-linking reaction. To obtain further information, complementary FTIR-ATR experiments were performed on the films prepared at different temperatures. Figure 1B shows the spectra from the films resulting from the photopolymerization, with those of both PMMA and EGDMA (with free double bonds) for comparison. A specific band can be identified at 812 cm−1 related to residual E
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has to be mentioned that the affinity of the monomer molecules for the cover is independent of the cover employed. Thus, the use of either hydrophilic or hydrophobic (obtained by silanization) covers yields similar wrinkle characteristics. This behavior, a priori unexpected, can be explained by taking into account the chemical structure of the monomer units that possess both hydrophobic and hydrophilic functional groups and therefore are able to wet both types of interfaces. Whereas the mechanism and the equilibrium between the two forces that are directly related to the temperature drive the formation of the wrinkles or the lack of formation, the experimental conditions employed for the film preparation clearly affect wrinkle formation. In particular, the role of film thickness, controlled by the spacer employed, and the MMA/ EGDMA composition of the feed were explored. Figure 3 shows the SEM and optical images of the surface wrinkles obtained with variable volume ratios of EGDMA (from 1 to 15%). Wrinkles were observed for a particular spacer (50 μm) in samples with a monomer composition with at least 5% (v/v) EGDMA. The level of volume contraction was rather low in the sample [only 1% (v/v)] and appeared to be insufficient to initiate the process. However, samples containing both 5 and
Scheme 3. Illustration of the Surface Wrinkles Obtained upon Simultaneous Heating and Photo-Cross-Linking and the Forces Involved in Their Formation
two different forces. On one hand, the volume contraction resulting from network construction during the cross-linking reaction led to the formation of cavities and enlarged them during the reaction. On the other hand, the attraction of the monomer molecules by the interface, i.e., capillary force, maintains the contact between the solution and the interface. It
Figure 3. SEM images and 3D optical micrographs of the surface patterns formed by photo-cross-linking of variable MMA/EGDMA volume ratios of (A) 99/1, (B) 95/5, and (C) 85/15 but using a 50 μm spacer. All the samples were photopolymerized with 2 wt % IRG 651 at 100 °C. The scale bar is 500 μm. F
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Figure 4. Average wrinkle dimensions: wrinkle period (left) and wrinkle amplitude (right) measured for films obtained using different spacers (from 50 to 150 μm). (A) The monomer mixture employed (MMA/EGDMA) was varied from 5 to 45% (v/v) EGDMA. (B) The monomer mixture employed (S/DVB) was varied from 5 to 45% (v/v) DVB. For these experiments undertaken at 100 °C, a constant amount of 2 wt % IRG 651 was employed.
homogeneously distributed wrinkles requires a minimal amount of cross-linking agent. Thus, to form more homogeneous wrinkles when using larger spacers, larger amounts of crosslinking monomer are desirable. For example, when using a 100 μm spacer, heterogeneous wrinkles with some planar areas were observed in samples containing
Versatile Approach for the Fabrication of Functional Wrinkled Polymer Surfaces Marta Palacios-Cuesta,† Marta Liras,†,§ Adolfo del Campo,‡ Olga García,*,† and Juan Rodríguez-Hernández*,† †
Department of Chemistry and Properties of Polymers, Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, Spain ‡ Instituto de Cerámica y Vidrio (ICV-CSIC), Kelsen 5, 28049 Madrid, Spain ABSTRACT: A simple and versatile approach to obtaining patterned surfaces via wrinkle formation with variable dimensions and functionality is described. The method consists of the simultaneous heating and irradiation with UV light of a photosensitive monomer solution confined between two substrates with variable spacer thicknesses. Under these conditions, the system is photo-crosslinked, producing a rapid volume contraction while capillary forces attempt to maintain the contact between the monomer mixture and the cover. As a result of these two interacting forces, surface wrinkles were formed. Several parameters play a key role in the formation and final characteristics (amplitude and period) of the wrinkles generated, including the formulation of the photosensitive solution (e.g., the composition of the monomer mixture) and preparation conditions (e.g., temperature employed, irradiation time, and film thickness). Finally, in addition, the possibility of modifying the surface chemical composition of these wrinkled surfaces was investigated. For this purpose, either hydrophilic or hydrophobic comonomers were included in the photosensitive mixture. The resulting surface chemical composition could be finely tuned as was demonstrated by significant variations in the wettability of the structured surfaces, between 56° and 104°, when hydrophilic and hydrophobic monomers were incorporated, respectively
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INTRODUCTION Surface instabilities have received particular attention because they can be employed to pattern polymer surfaces and generate a variety of nano- and microstructures. Surface instabilities produced in polymer films that have led to patterned surfaces include dewetting in thin films,1−8 phase separation of polymer blends or block copolymers, 9−11 the use of modified substrates,6,12,13 electric fields,14−18 or formation of surface wrinkles.19−23 While initially both buckling and wrinkling were considered as undesirable mechanical instabilities, our understanding of the mechanism of formation and the large amount of potential applications has stimulated interest in this particular approach to pattern polymer surfaces.24−27 As examples, wrinkled surfaces have been employed to prepare electrodes for electroactive28/conductive29 polymer actuators and anticorrosive coatings,30 to produce high-performance electronics on rubber substrates,31 and to produce surfaces with controlled wettability, for instance, with superhydrophilic22 or anisotropic wetting behavior on tunable surfaces.20 More recently, in combination with surface-nanopatterned substrates, anisotropic and hierarchically structured interfaces were obtained by Stafford and co-workers.27 Although the formation of wrinkles on a polymer surface has been achieved by different approaches,32−37 in general the fabrication of this particular type of surface pattern is accomplished using a soft material with low elastic moduli, © XXXX American Chemical Society
typically PDMS, as a substrate. During either mechanical stretching/compression or thermal expansion, a rigid layer (a metal,38,39 a polymer layer,28 or simple oxidation of the PDMS substrate40,41) is deposited on top of the material. Relaxation of the forces applied,42 heating,43 or cooling to room temperature38,44 induces, upon buckling, the formation of surface wrinkles. The first method reported used the evaporation of aluminum on a flexible substrate to form a rigid layer.38 The metal was spread on the thermally expanded PDMS layer (high temperature) that, upon cooling, contracts and induces the formation of wrinkles in the metallic layer. Other methods for obtaining a rigid layer involve the oxidation of the PDMS film with UV−ozone and plasma treatment.40,41 Depending on the conditions employed and the oxidative method, microstructures with surface wrinkles from 150 nm to several hundreds of micrometers can be obtained. However, the different mechanical resistance of the layer deposited compared to the bulk limits the lifetime of the wrinkles and may induce cracking on the surface formed. Moreover, the chemical composition is limited to selected metals, oxides resulting from surface treatments, or coatings with high-modulus polymers. Received: May 13, 2014 Revised: October 13, 2014
A
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fluorostyrene (5FS)] was included at variable ratios to produce functional wrinkles with variable dimensions with the aim of simultaneously controlling the chemical composition. This allowed buckled surfaces with a variable chemical composition to be generated depending on the initial monomer composition.
As an alternative to the aforementioned examples, recently several groups have described the formation of wrinkled interfaces, replacing the PDMS substrate with other polymeric coatings such as hydrogels or photo-cross-linkable systems.45,46 On one hand, confinement of hydrogels has been demonstrated to induce surface deformations that may lead to surface instabilities and finally to wrinkle formation.35,47−50 In these homogeneously cross-linked materials, the presence of a rigid support is responsible for the surface deformation. On the other hand, photo-cross-linkable systems are based on a vertical gradient in the cross-linking degree from the air−polymer interface to the polymer−support interface. Upon surface deformation, for instance, by swelling, the interface buckles and forms wrinkles. One of the most recently described approaches to forming wrinkled surfaces employs irradiation in two steps of an acrylate mixture.51 To create microstructures, the sample is irradiated with a monochromatic excimer lamp with a small penetration depth that polymerizes only the top layer of the photosensitive mixture. This gradually photopolymerized layer floats on the nonpolymerized mixture, and because of the volume contraction superficial wrinkles are formed. In a second step designed to fix the structure, the system is treated using through-curing irradiation with, for instance, a Hg lamp. As an illustrative example, Crosby et al.50 employed a mixture formed by acrylic monomers and a cross-linker and irradiated the mixture while applying a controlled oxygen flow on top of the sample. As mentioned above, wrinkles prepared, for instance, using a PDMS substrate allow fine-tuning of the wrinkle characteristics. However, variations in the chemical composition required the deposition of a functional layer. Equally, the microfolded surfaces obtained from hydrogels or photo-cross-linked materials have been employed using particular systems52 of acrylic monomers.50 These were conducted in two steps, and the wrinkle dimensions seem to be difficult to control. In addition, the pattern completely changes with a change in the formulation51 or is limited to a particular system,53 wrinkle formation requires a large amount of non-cross-linked monomer, and the unreacted monomer partially remains in the polymer film and needs to be removed to prevent further side reactions. In this work, we describe the elaboration of wrinkled surfaces with significant advantages over previous approaches52,54 based on the confinement of monomer mixtures between two interfaces varying the distance between them with a spacer. First, by using simultaneous photo-cross-linking and heating, functional wrinkled interfaces with variable buckle dimensions (amplitude and period) depending on the monomer/crosslinking agent ratio and the spacer employed were prepared in a single straightforward step. In addition, in this case, the reactive conversion is complete so that the presence of residual monomer, present in previously reported approaches, is avoided. Finally, monomer confinement between support and cover allowed the use of low-boiling point monomers that would evaporate if other approaches were employed. The mixture of a difunctional monomer [ethylene glycol dimethacrylate (EGDMA) for the acrylates and divinylbenzene (DVB) for styrenics] with a linear monomer [methyl methacrylate (MMA) or styrene (S)] was employed. First, we will describe the role of the temperature and thickness in wrinkle formation. Subsequently, functional acrylates [2hydroxyethyl methacrylate (HEMA) and trifluoroethyl methacrylate (TFMA)] or a styrene derivative monomer [penta-
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EXPERIMENTAL SECTION
Materials and Methods. Methyl methacrylate (MMA) was washed three times with a basic aqueous solution (10% NaOH) and three additional times with water. Then, the resulting monomer was dried on anhydrous magnesium sulfate, filtered, and distilled. Styrene (S) was dried under CaH2 and distilled under reduced pressure. Ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB), 2(hydroxyethyl methacrylate) (HEMA), 2,2,2-trifluoroethyl methacrylate (TFMA), and 2,3,4,5,6-pentafluorostyrene (5FS) (all from Aldrich with the highest purity); Irgacure 651 (IRG 651) and 2,2-dimethoxy1,2-diphenylethan-1-one (Ciba); and dichlorodimethylsilane (Aldrich, 98.5%) and the rest of the solvents were employed as received without further purification. Silicon wafers (Siegert Consulting e.k.) and 0.15 mm thickness glass covers (Menzel-Glaser) were employed as supports. Infrared spectra were recorded using a Spectrum One FTIR spectrometer (PerkinElmer) fitted with a horizontal attenuated total reflectance (ATR) accessory under unforced conditions. The irradiated samples were placed in direct contact with the diamond crystal with no previous preparation. Spectra were collected at 8 cm−1 resolution by co-adding six scans per spectrum. Scanning electron microscopy (SEM) was used for surface structural and cross-sectional analysis. Micrographs were taken using a Philips XL30 instrument with an acceleration voltage of 25 kV. The samples were coated with gold and palladium (80/20) prior to scanning. Cross sectional profiles and three-dimensional (3D) images of the wrinkled surfaces were characterized by using a Zeta-20 True Color 3D Optical Profiler from Zeta Instruments. Methodology for Preparing the Wrinkles. Photosensitive mixtures contained variable amounts of a cross-linking agent, i.e., ethylene glycol dimethacrylate (EGDMA) for the methacrylic monomers and divinylbenzene (DVB) for the styrenics and the corresponding linear monomers. The methacrylic linear monomers employed throughout this study were methyl methacrylate (MMA), 2hydroxyethyl methacrylate (HEMA), and 2,2,2-trifluoroethyl methacrylate (TFMA) in different ratios and were copolymerized with EGDMA. The styrenic monomers employed were styrene (S) and 2,3,4,5,6-pentafluorostyrene (5FS) and were copolymerized with DVB. In addition, a radical photoinitiator, IRG 651 (2 wt % with respect to the total amount of monomers), was employed to start the polymerization process. The photopolymerization of the films was undertaken under a UV spotlight irradiation source using a Hamamatsu model Lightning Cure L8868 instrument provided by a 200 W Hg−Xe lamp. To prepare the films, 2 cm × 2 cm silicon wafers with variable spacers (50−150 μm) were employed. A few drops of the photosensitive mixture were placed in the center of the wafer and covered with 0.30 mm thick glass. The samples were preheated on a hot plate and irradiated under constant heating. The incident light was focused on the samples with an optical fiber (sample−light distance fixed at 8 cm), and the irradiation intensity was kept constant at 6150 mW/m2 (measured by a Luzchem SPR-01 radiometer) throughout the experiments. Initial tests were conducted by varying the ratio of linear monomer versus cross-linking agent to optimize wrinkle formation. The samples having additionally functional monomers were prepared using a constant ratio of linear monomers (i.e., both functional monomer and nonfunctional monomer) and cross-linking agent of 85/15 (v/v).
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RESULTS AND DISCUSSION Mechanism of Wrinkle Formation. Wrinkled topographies were prepared using the setup described in Scheme
B
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Scheme 1. (A) Illustration of the Experimental Procedure Used To Fabricate Wrinkled Surfaces for MMA/EGDMA/IRG Mixturesa and (B) a 3D Image Obtained by Using an Optical 3D Optical Profiler That Corresponds to a Photosensitive Mixture (C) Containing 85% (v/v) Monomer (MMA), 15% (v/v) Cross-Linking Agent (EGDMA), and 2 wt % Photoinitiator (IRG 651)
a
The sample is irradiated and heated. During this process, volume contraction and capillary forces act simultaneously inducing the formation of wrinkled interfaces.
Scheme 2. Chemical Structures of the Monomers, Cross-Linking Agents, and the Photoinitiator Employed in This Studya
a
We explored two different families of monomer/cross-linking agent mixtures: (A) methyl methacrylate/EGDMA and (A′) styrene/DVB. Additionally, monomers MMA and S in the mixture have been partially or completely substituted with other functional monomers (B and B′, respectively) to vary the chemical composition of the wrinkled interface.
1. The monofunctional monomer (MMA) was mixed with the cross-linking agent [ethylene glycol dimethacrylate (EGDMA)] and the photoinitiator (IRG 651), and the mixture was confined in a closed chamber. The liquid mixture was then simultaneously heated and irradiated using UV light that could pass through the glass cover employed. After irradiation for 4
min, the reaction was completed and the cover removed. The use of a cover avoids monomer evaporation, thus assuring that the composition of the final material is identical to the feed composition. Moreover, a planar cover limits variations in thickness over the sample and favors the homogeneity of the surface pattern. As a result of the simultaneous irradiation and C
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Figure 1. (A) Optical micrographs of the surface patterns formed by photo-cross-linking of the MMA/EGDMA mixture [85/15 (v/v)] and 2 wt % IRG 651 at different temperatures (50, 70, 90, and 100 °C). The monomer mixture was allowed to reach the desired temperature prior to irradiation. The scale bar is 500 μm. (B) FTIR-ATR spectra (left) of the cross-linked films obtained by simultaneous heating and UV irradiation of the MMA/ EGDMA monomer mixture [85/15 (v/v)] at different temperatures. Representation of the Band I/Band II ratio (right) as a function of the photocross-linking temperature employed.
different families of monomers, i.e., acrylics and styrenics, that may provide materials with different surface wettabilities, for example. In the EGDMA/MMA mixture, the MMA was partially or totally substituted with a functional monomer: either hydrophilic (HEMA) or hydrophobic (TFMA). Equally for the DVB/S mixture, the linear monomer, i.e., styrene, was
photo-cross-linking, wrinkled structures such as the example shown in Scheme 1B were observed. The approach illustrated in Scheme 1 has been extended to other monomers to demonstrate the versatility of this strategy. More precisely, Scheme 2 shows the chemical structures of monomers, cross-linking agents, and the photoinitiator employed throughout this study. We have explored two D
dx.doi.org/10.1021/la502913w | Langmuir XXXX, XXX, XXX−XXX
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Figure 2. Optical micrographs of the formation of wrinkles at different polymerization stages: (A) initial monomer mixture, (B) formation of nucleation points, (C) extension of the nucleation, and (D) final formation of wrinkles.
double bonds of the acrylic functionality (−CHCH− twisting). At low temperatures, a relatively large amount of residual double bonds is present in the film upon photopolymerization. Nevertheless, with an increase in temperature the intensity of the −CC− signal decreases while the −C− C− band observed at ∼840 cm−1 is relatively more intense. We can thus conclude that increasing the temperature increases the level of effective cross-linking. The amount of residual −C C− is reduced, producing an increase of the volume contraction upon UV irradiation. In addition, Figure 1B exhibits the ratio of Band I and Band II as a function of the photo-cross-linking temperature employed. This explains, at least to some extent, not only the formation of wrinkled interfaces but also why surface wrinkles were produced to a larger extent when the reaction was conducted at higher temperatures. According to the optical profiler images depicted in Figure 2, obtained at different reaction stages, wrinkle formation may occur as follows. The initial monomer mixture fills the volume between the covers. When the photopolymerization starts, as a consequence of volume contraction, cavities with rather irregular dimensions are formed (Figure 2B). The polymerization continues, and as a consequence of volume contraction, an enlargement of the cavities is observed (Figure 2C). As a result of this process, the cavities interconnect before the completion of the reaction and produce a completely wrinkled film. According to these experimental observations, we can hypothesize that wrinkle formation might be the result of interplay between two different forces acting simultaneously. In Scheme 3 are depicted the 3D images of a wrinkled surface (A) and a cross section of a particular wrinkle (B). The characteristic wrinkle profile also confirmed the presence of
partially or totally replaced with HEMA (hydrophilic) or 5FS (hydrophobic). However, before the variations in surface functionality were explored, the experimental conditions for performing the photopolymerizations were optimized. Initially, the photopolymerization reactions were undertaken at different temperatures, and the surface patterns were observed to change dramatically as a function of the temperature employed. The samples were irradiated with UV light while heating was maintained for 4 min. The micrometer size surface features formed using MMA [85% (v/v)] and EGDMA [15% (v/v)] using 2 wt % IRG 651 as a photoinitiator are depicted in Figure 1A. Whereas for temperatures from room temperature to 70 °C no significant, or only partial, wrinkle formation was observed, at 100 °C the formation of micrometer-sized wrinkles was quite homogeneous over the entire film. It should be mentioned that in the case of styrene/DVB mixtures the temperature required to observe the formation of wrinkled interfaces was 140 °C. Indeed, the photopolymerization kinetics of the S/DVB mixture was slow in comparison to that of the MMA/ EGDMA mixture, and additional heating was required. It should be mentioned at this point that the monomer conversion achieved is almost complete. Analysis conducted by washing the films with organic solvents to extract residual monomer and further analysis by nuclear magnetic resonance confirmed the complete consumption of the monomers in the photo-cross-linking reaction. To obtain further information, complementary FTIR-ATR experiments were performed on the films prepared at different temperatures. Figure 1B shows the spectra from the films resulting from the photopolymerization, with those of both PMMA and EGDMA (with free double bonds) for comparison. A specific band can be identified at 812 cm−1 related to residual E
dx.doi.org/10.1021/la502913w | Langmuir XXXX, XXX, XXX−XXX
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has to be mentioned that the affinity of the monomer molecules for the cover is independent of the cover employed. Thus, the use of either hydrophilic or hydrophobic (obtained by silanization) covers yields similar wrinkle characteristics. This behavior, a priori unexpected, can be explained by taking into account the chemical structure of the monomer units that possess both hydrophobic and hydrophilic functional groups and therefore are able to wet both types of interfaces. Whereas the mechanism and the equilibrium between the two forces that are directly related to the temperature drive the formation of the wrinkles or the lack of formation, the experimental conditions employed for the film preparation clearly affect wrinkle formation. In particular, the role of film thickness, controlled by the spacer employed, and the MMA/ EGDMA composition of the feed were explored. Figure 3 shows the SEM and optical images of the surface wrinkles obtained with variable volume ratios of EGDMA (from 1 to 15%). Wrinkles were observed for a particular spacer (50 μm) in samples with a monomer composition with at least 5% (v/v) EGDMA. The level of volume contraction was rather low in the sample [only 1% (v/v)] and appeared to be insufficient to initiate the process. However, samples containing both 5 and
Scheme 3. Illustration of the Surface Wrinkles Obtained upon Simultaneous Heating and Photo-Cross-Linking and the Forces Involved in Their Formation
two different forces. On one hand, the volume contraction resulting from network construction during the cross-linking reaction led to the formation of cavities and enlarged them during the reaction. On the other hand, the attraction of the monomer molecules by the interface, i.e., capillary force, maintains the contact between the solution and the interface. It
Figure 3. SEM images and 3D optical micrographs of the surface patterns formed by photo-cross-linking of variable MMA/EGDMA volume ratios of (A) 99/1, (B) 95/5, and (C) 85/15 but using a 50 μm spacer. All the samples were photopolymerized with 2 wt % IRG 651 at 100 °C. The scale bar is 500 μm. F
dx.doi.org/10.1021/la502913w | Langmuir XXXX, XXX, XXX−XXX
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Figure 4. Average wrinkle dimensions: wrinkle period (left) and wrinkle amplitude (right) measured for films obtained using different spacers (from 50 to 150 μm). (A) The monomer mixture employed (MMA/EGDMA) was varied from 5 to 45% (v/v) EGDMA. (B) The monomer mixture employed (S/DVB) was varied from 5 to 45% (v/v) DVB. For these experiments undertaken at 100 °C, a constant amount of 2 wt % IRG 651 was employed.
homogeneously distributed wrinkles requires a minimal amount of cross-linking agent. Thus, to form more homogeneous wrinkles when using larger spacers, larger amounts of crosslinking monomer are desirable. For example, when using a 100 μm spacer, heterogeneous wrinkles with some planar areas were observed in samples containing
