Acs Langmuir 8b01965

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Interface Components: Nanoparticles, Colloids, Emulsions, Surfactants, Proteins, Polymers

Effect of Varying the Chain Length and Content of Poly(dimethylsiloxane) on
the Dynamic De-wetting Performance of NP-GLIDE Polyurethane Coatings
Emily Gee, Guojun Liu, Heng Hu, and Jiandong Wang
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b01965 • Publication Date (Web): 28 Jul 2018
Downloaded from http://pubs.acs.org on August 2, 2018
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Page 1 of 35 Langmuir
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Effect of Varying the Chain Length and Content of Poly(dimethylsiloxane) on the
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6 Dynamic De-wetting Performance of NP-GLIDE Polyurethane Coatings
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9 Emily Gee, Guojun Liu*, Heng Hu, and Jiandong Wang
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11 Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario Canada K7L
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13 3N6 email: gliu@chem.queensu.ca
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18 Abstract. NP-GLIDE polyurethane (PU) coatings are prepared by curing a commercial polyol
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20 P0, a hexamethylene diisocyanate trimer (HDIT), and P1-g-PDMS, which is a graft copolymer
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consisting of a polyol backbone P1 bearing poly(dimethylsiloxane) (PDMS) side-chains. These
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25 materials are known as NP-GLIDE because most test liquids have no problem to cleanly glide
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27 off them and because segregated nanopools of a grafted lubricating ingredient (PDMS) for
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29 dewetting enablement are dispersed throughout the coating matrix. To optimize the de-wetting
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32 performance of the NP-GLIDE coatings, the molecular weights of the PDMS side chains in the
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34 P1-g-PDMS samples were increased from 1.0 kDa (1k) to 5.0 kDa (5k) and 10.0 kDa (10k). A
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36 comparative study of coatings containing the three different P1-g-PDMS samples at a constant
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39 PDMS mass fraction of either 6.0 or 2.00% (m/m) showed that the P1-g-PDMS5k-based coatings
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41 exhibited the best de-wetting properties. These properties included the lowest sliding angles for
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43 test liquids that were incompatible with PDMS and the fastest and most effective contraction of
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marker ink traces and a paint. Coatings containing 0.50 and 1.00% (m/m) of PDMS5k were also
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48 prepared from P1-g-PDMS5k and were compared with those containing 2.00 and 6.0% (m/m) of
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50 PDMS5k. The coatings were shown to retain their de-wetting properties with PDMS contents as
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52 low as 1.00% (m/m). While the results of this study provided valuable insight regarding the
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60 ACS Paragon Plus Environment
Langmuir Page 2 of 35
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3 design of future practical NP-GLIDE coatings, a model has also been proposed for the surface
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6 structure of the coatings to justify our observations.
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10 Keywords: Coatings, Omniphobicity, Polyurethane, Slippery Surfaces
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15 I. Introduction
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17 Transparent and durable omniphobic coatings that repel oil- and water-borne contaminants
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are highly desirable. Such a coating can impart self-cleaning performance to a windshield, thus
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22 improving visibility for a driver on a rainy day. On a cell phone, it reduces the deposition of
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24 sweat, fingerprints, and other liquid-based stains. These materials may also find applications in
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26 preventing fouling on the hulls of ships or on medical devices.
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29 One approach to fabricate omniphobic coatings is to create coarse low-surface-tension
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31 surfaces with roughness on the nanometer and micrometer scales.1-14 For oil repellency, re-
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33 entrant features, which are surfaces hidden under overhangs and include the bottom half of a
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sphere or the gills of a mushroom, are also required.1, 15 On such a surface, droplets of test
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38 liquids may hang above protrusions of the surface, existing in the so-called Cassie-Baxter state.16
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40 In this state, even test liquids such as hexadecane, which has a low surface tension of 27.5 mN/m
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at room temperature, may exhibit contact angles exceeding 150°.11, 15 Moreover, the droplets
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45 may easily roll off the surface at low tilting angles because the contact area and thus the number
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47 of interacting sites between the protrusions and the droplets are low and the adhesion between
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49 them is weak.1, 11
Drawbacks of this approach include the fragility of the nanometer- and
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52 micrometer-sized surface features and their scattering of light which renders opacity to the
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54 coating.9-10, 13
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3 An alternative approach is to generate a porous or rough surface first and then fill the pores
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6 or voids between protrusions with a liquid lubricant, yielding a slippery liquid-infused porous
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8 surface (SLIPS).17-21 The lubricant should have a high affinity for the pore surfaces to ensure
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10 that it is imbibed. Meanwhile, if the over-flowing lubricant is to repel both water and
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hydrocarbon-based oils and remain with the porous surface, it should be incompatible with the
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15 test liquids. This essentially limits the choice of lubricants to fluorinated liquids. An
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17 incompatible test liquid slides well on a SLIPS because the friction coefficient between the test
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liquid and the pore-filling liquid is low. However, fluorinated reagents are expensive and are not
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22 necessarily environmentally friendly. Moreover, the unbound lubricant may be lost via
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24 evaporation or due to its solubility in liquids with which it comes into contact.
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26 An omniphobic coating may be created via a third approach by covalently attaching or
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29 grafting chains of a liquid polymer such as poly(dimethyl siloxane) (PDMS) by one end onto a
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31 surface, yielding a liquid-like monolayer.22-25 This layer is liquid-like rather than purely liquid
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33 because chains in this layer cannot flow from one location to another. Instead, a chain undergoes
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wriggling, stretching, retracting, and other motions within a circle centered around its grafting
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38 site and the radius of this circle would be smaller than the fully stretched length of the chain.
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40 Despite the reduced freedom of motion of these grafted chains, this liquid-like layer still offers
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superior liquid sliding performance. The additional advantage is that the grafted layer is not
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45 swept away even if it is placed under the flow of a compatible test liquid. Potential drawbacks of
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47 this approach include the need to tailor the grafting chemistry for different substrates.
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49 Inspired by the SLIPS and the monolayer coating designs, our group has developed NP-
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52 GLIDE coatings that contain nanopools of a grafted lubricating ingredient for dewetting
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54 enablement. In this approach, 4 - 8% (m/m) of a low surface tension liquid polymer, such as a
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3 perfluorinated polyether26 or PDMS,27-32 is tethered by one end to one component of a
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6 polyurethane (PU), epoxy, or UV-curable coating formulation. To prepare a PDMS-modified
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8 NP-GLIDE PU coating, for example, PDMS is tethered onto a reactive oligomeric polyol to
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10 yield a graft copolymer polyol-g-PDMS, where g denotes graft. Polyol-g-PDMS is then cured
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together with an unmodified polyol using a polyisocyanate. PDMS does not undergo
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15 macrophase separation from the matrix during the coating formation and curing process because
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17 it is added as a graft copolymer and is covalently bound to a polyol backbone. However, due to
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its incompatibility with the coating matrix, PDMS still undergoes microphase separation to form
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22 spherical domains that are dispersed throughout the matrix as nanopools. These spherical
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24 nanopools consisting of the grafted liquid polymer bear structural resemblance to the pores that
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26 contain a free lubricant in a SLIPS coating. In addition, the liquid polymer in an NP-GLIDE
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29 coating enriches itself on the surface to presumably form a liquid-like monolayer, rendering the
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31 dynamic de-wetting properties of the traditional monolayers.
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33 The NP-GLIDE coatings are transparent and useful for various substrates. The coatings are
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transparent because the nanopools formed by the liquid lubricant have diameters < 30 nm and
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38 thus do not scatter much light. The coatings bind strongly to many substrates because the
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40 lubricant is added in amounts that are typically less than 6.0% (m/m), which is too low to affect
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the interfacial binding chemistry between the matrix polymer and the substrate.
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45 While our prior research26-31 and research of others33-36 have focused on the development of
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47 various NP-GLIDE formulations, a systematic study of factors affecting the dynamic de-wetting
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49 properties of these coatings has not been reported. For example, only one PDMS sample with a
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52 number-average molecular weight of 5.0 kDa has been tested so far by us in all of the previously
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54 developed PDMS-based NP-GLIDE coatings and the possibility of further improving the
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3 properties of the coatings by changing the molecular weight of the PDMS component remains
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6 unexplored. In addition, the end-functionalized PDMS was substantially more expensive than
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8 the isocyanate or polyol components used in a PU coating, for example, and our previous coating
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10 formulations have used at least 4.0% (m/m) of PDMS. However, the excessive use of PDMS
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would increase the costs of the final coatings and hinder their wide-spread adoption by industrial
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15 stakeholders. Consequently, knowledge of the lowest amount of PDMS required to yield the
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17 targeted de-wetting properties is key to enhancing the commercial viability of these coatings.
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Therefore, the objectives of this study are to investigate the effect of varying the molecular
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22 weight and the PDMS content on the de-wetting properties of a NP-GLIDE PU coating
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24 formulation. We believe that the results described herein will provide valuable insight and
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26 guidance for the development of other PDMS-based NP-GLIDE coatings.
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31 II. Results and Discussion
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33 The coatings were prepared by curing cast films of a hexamethylene diisocyanate trimer
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(HDIT, Scheme S1a in the SI), a commercial polyol P0, and a graft copolymer P1-g-PDMS
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38 (Scheme S1b), where the polyol P1 was tailor-made for this project. The molecular weight of
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40 the PDMS side chains in the graft copolymers P1-g-PDMS changed from 1.0 kDa to 5.0 and
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10.0 kDa, respectively. Other details about the preparation and properties of the coating
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45 precursors and the coatings are provided in the SI.
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47 Optical Transparency and Internal Structures of the Coatings. The coatings used in
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this study all had a thickness of 30 ± 1 µm, as calculated from the mass of solid precursors cast
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52 on unit surface area of the glass substrate. Regardless of the P1-g-PDMS samples used and the
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58 5
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3 final PDMS contents ranging between 0.50 and 6.0% (m/m), the coatings were highly transparent
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6 and had transmission values exceeding 99% at 500 nm.
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Figure 1. Cross-sectional AFM topography images of coatings that contained 6.0% (m/m) of
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PDMS and were prepared from (a) P1-g-PDMS1k, (b) P1-g-PDMS5k, and (c) P1-g-PDMS10k,
44 respectively. Also shown for comparison is an image (d) of a P1-g-PDMS5k-based
45 coating that contained 1.00% (m/m) of PDMS.
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47 We have previously ascribed the high transparency to the segregation of PDMS inside the
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50 coating matrix into small nanopools, which did not scatter much light.26-27, 29 Figure 1 compares
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52 the atomic force microscopy (AFM) topography images showing cross-sections of coatings
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54 containing 6.0% (m/m) of PDMS derived from P1-g-PDMS1k, P1-g-PDMS5k, and P1-g-PDMS10k,
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3 respectively. The nanopools seen in these images all had diameters less than 10 nm. Thus, the
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6 same explanation could be used to account for the observed high optical clarity of these samples.
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8 Figure 1d shows a cross-sectional AFM image of a coating containing 1.00% (m/m) of
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10 PDMS5k. Figures 1b and 1d suggest that the pool density decreased as the PDMS5k content was
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reduced from 6.0 to 1.00% (m/m), as predicted.
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15 Coating Surface Structure. Based on a flawed AFM image or sample, we have previously
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17 proposed that the NP-GLIDE coating surfaces also contained PDMS nanopools.29 To
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accommodate the higher density of surface-stratified PDMS chains, PDMS nanoditches (Scheme
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22 1a) occurred. The nanopools and nanoditches were postulated to be separated by ridges of the
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24 matrix polymer (formed by HDIT and P0, for example). In air, the exposed PDMS chains would
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26 stretch from their hosting nanopools and nanoditches to cover the ridges, thus decreasing the
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29 system’s overall surface energy.
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40 Scheme 1. Cross-sectional view of (a) the original and (b) the new model for NP-GLIDE coatings in the
41 dry state under air. Schemes (c) and (d) show the surface structures of the coating under hexadecane and
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water, which are good and poor solvents for PDMS, respectively.
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46 We now suspect that our original model was incorrect and propose that a dry surface
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48 consists of a PDMS monolayer containing occasional nanometer- or sub-nanometer-sized dents
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51 (Scheme 1b). These dents occur in regions where the PDMS chains are more sparsely
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53 distributed as depicted in Scheme 1c and the large spacings occur statistically. To help visualize
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55 the different chain spacings, we have further illustrated in Scheme 1c the conformations of the
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3 surface chains under a good solvent for PDMS. The PDMS chains are shown to emerge only
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6 from sites occupied by P1-g-PDMS but not by P0 or HDIT. The number of PDMS chains
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8 emanating from a site depends on the number of PDMS side chains attached to each P1 chain in
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10 P1-g-PDMS. In addition, the PDMS chains are not necessarily completely exposed and can be
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partially buried within the coating matrix. Moreover, the coating surface is not necessarily
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15 perfectly smooth but likely contains protrusions. Therefore, the average thickness of the solvent-
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17 swollen brush depends on the molecular weight of PDMS, the extent of chain burial in the
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coating matrix, and the stretching degree for the exposed segments of the PDMS chains. The last
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22 variable is in turn governed by the density of the exposed PDMS chains (number of chains per
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24 unit area) or the stratification degree of P1-g-PDMS. The thickness of the PDMS layer evidently
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26 decreases after the solvent evaporates and the brush collapses into a dry layer (Scheme 1b). We
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29 additionally assume that exposing such a dry layer to water, which has a greater compatibility
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31 with the PU matrix, may cause the PDMS chains to retreat from regions where they are sparsely
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33 populated, yielding pinholes that provide sites of contacts between PU and water (Scheme 1d).
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The newly proposed surface model was based on our recent AFM experiments. While
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38 Figures 2a-2c compare phase images obtained by tapping-mode AFM for the surfaces of the
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40 PDMS-free PU coating and NP-GLIDE coatings containing 6.0% (m/m) of PDMS5k and
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PDMS10k, Figure 2d shows an AFM topography image of the sample containing PDMS5k. One
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45 notes that the AFM phase and topography images (Figures 2b and 2d, respectively) of the
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47 PDMS5k-containing coating resembled each other. Such a resemblance was also seen for the
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49 phase and topography images of the PDMS-free PU sample or of the sample containing 6.0%
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52 (m/m) PDMS10k. Only the phase images rather than the topography images were shown for the
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54 latter two samples because the “peaks”, “ridges”, and “rims” exhibited stronger contrast with the
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3 valleys in the phase images. Here the valleys refer to the hemispherical wells surrounded by the
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6 rims and the other irregularly-shaped “depressions” among the peaks, ridges, or a combination of
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8 the two. Regardless of the images presented, the key finding was that the AFM images appeared
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10 similar for all of the samples regardless of the presence of PDMS or its molecular weight.
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47 Figure 2. AFM phase images of a) PU base coating and NP-GLIDE coatings containing
48 6.0% (m/m) of b) PDMS5k and c) PDMS10k as well as an AFM topography image
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d) of the NP-GLIDE coating containing 6.0% (m/m) of PDMS5k.
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53 The similarity between the phase and topography images of a sample suggests that the
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55 nanoscale differences in the surface height rather than the differences in the surface composition
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1
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3 gave rise to the contrast observed in the phase images. The phase angle of the AFM cantilever
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6 lags behind that of the oscillating force that sets the cantilever in motion because of the
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8 interaction between the cantilever and the surface that is under investigation.37-38 The magnitude
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10 of the phase delay increases as both the contact area that the cantilever tip makes with the surface
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and the Young’s modulus of the surface increase.37-38 A height difference can result in different
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15 degrees of phase lagging because the interaction area between the tip and the sample can change
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17 as the tips moves from the valley to the peak regions due to the finite size and shape of the tip.
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We do not know the exact reason why the surface roughness developed. We note from
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22 Figure 2d that the height fluctuations from region to region were within 10 nm. Such small-scale
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24 roughness could have been caused by slight differences in the rates of solvent evaporation or PU
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26 curing. For example, the faster vitrification or curing of the coating in one region could have
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29 created a protrusion at that location.
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31 The new model could easily justify the similarity between the AFM images of the samples
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33 regardless of the presence or the molecular weight of PDMS because the surface roughness may
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have existed in the PU coating itself. The minor differences among various samples arose from
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38 the effect that the randomly-distributed nanometer- or sub-nanometer-sized depressions in the
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40 PDMS layer had on the AFM images and from the influence that the PDMS layer had on the
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formation of the PU surfaces. In contrast, the old model could not explain the AFM data because
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45 the PDMS-free PU sample should be much smoother than the PDMS-bearing samples.
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47 According to Scheme 1a, the PDMS-containing coatings should have phase and tomography
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49 images that would have been much different from those of the PDMS-free PU coating.
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52 Aside from the AFM data, other experimental results also called for the new model. For
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54 example, we have monitored how the contact angle (CA) of a 15-µL water droplet residing on a
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3 coating containing 6.0% (m/m) of PDMS5k changed with time after it had been dispensed onto
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6 the surface. In one experiment, the CA decreased from 105.7° to 105.3° within 30 s. Between
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8 30 s and 4 min, the CA remained essentially constant (Figure 3).
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25 Figure 3. Variation in the contact angles of 15 µL of a water droplet
26 on a coating containing 6.0% (m/m) of PDMS5k.
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30 Several surface reconstruction phenomena could have accounted for the initial decrease in
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32 the water droplet’s CA. First, the functional groups that contacted water could have been
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34 changed (e.g., from the methyl groups of -Si(CH3)2- to the oxygen moieties of DMS units)
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37 during this time interval. Alternatively, some water/PU contacts could have formed. In terms of
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39 the old model, water/PU contacts were formed due to the retraction of PDMS chains from the PU
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41 ridges into their hosting surface nanopools and nanoditches. According to the new model, the
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number of water/PU contact points increased due to pinhole formation in the exposed PDMS
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46 layer.
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48 We argue for the possibility of the second surface reconstruction process by estimating the
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time required for the PDMS chains to retract into their hosting nanopools or nanoditches in the
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53 old model or for pinhole formation in the PDMS layer in the new model. Guillet and coworkers
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55 reported the diffusion coefficient D of ~10-6 cm2/s for the ends of poly(methyl methacrylate)
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3 chains with a molecular weight of ~104 Da in ethyl acetate.39-41 The more flexible PDMS5k
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6 chains in our study may have end-group D values greater than 10-6 cm2/s under identical
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8 conditions. However, the value should decrease in a thin pure PDMS5k layer. Still using 10-6
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10 cm2/s, the time required for the PDMS end groups to retract a distance d of ~10 nm from the PU
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13 ridges was estimated from ⁄2 to be 0.5 µs.42 Thus, this process should be fast and occur
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15 within seconds.
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17 While both the old and new model could be used to explain the initial CA decrease, the old
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20 model failed in explaining the extent of the CA decrease during this process. The old model
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22 suggests that the PU ridges accounted for a large fraction (e.g., 30% or more) of the coating
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24 surface area. At a fractional ridge surface area Φ of 30%, the water contact angle θ on the
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27 reconstructed surface could be calculated using eq. 1:43
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= Φ
+ 1 − Φ
(1)
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31 where and denote the Young’s CAs for water on the PU ridge and pure PDMS,
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34 respectively. Performing this calculation using the value30 of 83° and the value23, 25, 30 of
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36 108° yielded θ = 100°. Such a low θ value was not consistent with the experimental value of
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105.3° seen in Figure 3 or the values to be reported later on. In contrast, the new model suggests
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41 that the contact points between PU and water were increased due to pinhole formation. Since the
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43 pinhole fractional surface area would be low, the observed high equilibrium water CA was thus
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45 reasonable for the new model.
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48 The new model additionally explains the retention of the de-wetting properties of the NP-
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50 GLIDE coatings after being soaked under water for hours. After the formation of the initial
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52 pinholes, the further deterioration of the de-wetting properties of the coatings would require the
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surface PDMS chains to withdraw into the PU coating matrix. This process can be restricted
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3 both kinetically and thermodynamically. The old model cannot explain the long-term de-wetting
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6 properties of the NP-GLIDE coatings. After water has come into contact with the PU ridges
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8 within a few seconds or less, water droplets should become pinned and lose their ability to slide.
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10 De-Wetting Behaviour of Different Test Liquids. Coatings containing 6.0% (m/m) PDMS
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were prepared using P1-g-PDMS1k, P1-g-PDMS5k, or P1-g-PDMS10k as the de-wetting enabler
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15 and the de-wetting behavior of various test liquids on these surfaces was assessed by measuring
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17 the liquids’ CAs, sliding angles (α), as well as the advancing and receding contact angles and
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20 , which were then used to calculate the contact angle hysteresis (∆ = − . For the CA
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22 measurements, 5 µL droplets were used and the measurements were made between 30 s and 1
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24 min after a droplet had been dispensed on a coating. Three to four samples were analyzed for
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27 each formulation and each sample was used to yield the CAs of two to three droplets in different
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29 regions. For α and ∆ measurements, one to two droplets were tested per sample and three to
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31 four samples were prepared for each formulation. The gathered data were then used to calculate
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34 the averages and standard deviations. While the CA and α values of all test liquids except water
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36 were measured using 5 µL droplets, 15 µL droplets were used for the measurements of the α
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values of water because the smaller water droplets did not readily slide. Table 1 shows the data
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41 obtained for the coatings containing PDMS with different molecular weights.
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44 Table 1. Effect of varying the molecular weight of PDMS on the CA, α, and ∆θ values of
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46 various test liquids on coatings containing 6.0 wt % of PDMS.
47 Test γ a (mN/m) CA (o) α (o) ∆θ (o)
Liquid
48 PDMS1k PDMS5k PDMS10K PDMS1k PDMS5k PDMS10K PDMS1k PDMS5k PDMS10K
Liquids that are miscible with PDMS
49 Hexadecane 27.5 34 ± 1 33 ± 2 35 ± 1 6±1 5±1 3±1 2±1 4±1 2±1
50 THF 26.4 24 ± 1 25 ± 1 25 ± 1 5±1 2±1 3±2 2±1 1±1 1±1
51 Dodecane 25.4 20 ± 1 20 ± 1 17 ± 1 3±1 2±1 3±1 3±1 3±1 3±1
52 Decane 23.8 15 ± 2 15 ± 1 16 ± 1 3±1 2±1 2±1 2±1 2±1 3±1
Octane b 21.6 4±1 7±2 8±2 5±1 3±1 6 ±1 2±2 2±1 1±1
53 Silicone Oil c 19.0 3±1 4±2 5±3 N/A N/A N/A N/A N/A N/A
54 Liquids that are immiscible with PDMS
55 Water 72.8 105 ± 1 107 ± 1 105 ± 1 32 ± 4 17 ± 2 40 ± 4 13 ± 2 7±2 18 ± 1
56 Diiodomethane 50.8 75 ± 2 76 ± 1 77 ± 1 11 ± 3 7±2 17 ± 2 14 ± 1 10 ± 2 20 ± 1
57
58 13
59
1
2
3 DMF 37.1 63 ± 1 65 ± 1 63 ± 1 36 ± 1 31 ± 1 37 ± 4 15 ± 2 13 ± 1 16 ± 1
4 Methanol b 22.7 34 ± 2 35 ± 1 33 ± 2 19 ± 3 14 ± 2 31 ± 3 9±1 6±2 9±2
5 Ethanol b 22.1 34 ± 2 36 ± 2 35 ± 2 16 ± 2 14 ± 1 24 ± 2 9±1 8±2 11 ± 1
a o b
6 : Surface tension data at 20 C obtained from http://www.surface-tension.de/. : Measured
7 values may have relatively large errors due to solvent volatility and changes in the droplet
8 volume during measurement. c: The Mn of the silicone oil is 2.0 kDa.
9
10
11
12 The test liquids shown in Table 1 were divided into two groups: those that were either
13
14 miscible or immiscible with PDMS. In classifying the solvents, PDMS solubility data reported
15
16 by Whitesides and coworkers were used as a guide.44 Since the compatibility of diiodomethane
17
18
19
with PDMS was not reported in the Whitesides paper, we independently determined their
20
21 compatibility. We discovered that 2.0 mg of PDMS5k or PDMS10k was insoluble in 0.10 mL of
22
23 diiodomethane. Thus, diiodomethane and PDMS were incompatible.
24
25
The data show that the CAs of the test liquids in a given group decreased as their surface
26
27
28 tension γ decreased. This trend could be justified by Young’s equation,42 which suggests that
29
30 liquids with lower surface tensions γ are more likely to spread than those with higher γ.
31
32
33 The data also show that the α and ∆ values initially decreased as γ of the test liquid in a
34
35 given series decreased. For the series of PDMS-incompatible test liquids, the exception was
36
37
diiodomethane, which has a γ value of 50.8 mN/m, which exceeds 37.1 mN/m for N,N-dimethyl
38
39
40 formamide (DMF). However, the α and ∆ values of diiodomethane were lower than those of
41
42 DMF. A similar phenomenon was observed in the series of PDMS-compatible liquids, where the
43
44
45 α and ∆ values initially decreased with decreasing γ but increased from decane to octane after γ
46
47 decreased below a critical value of ~ 23.8 mN/m. Silicone oil, with the lowest γ value of 19.0
48
49
mN/m, was also unable to slide cleanly on the coatings.
50
51
52 The above trends can be explained by eq. 2:45
53
54
sin = cos − cos (2)
55
56
57
58 14
59
1
2
3 where denotes the surface tension of a test liquid; mg represents the weight of the test liquid
4
5
6 droplet, and w is the base diameter of the droplet on the coating. According to eq. 2, α and ∆
7
8 would decrease as decreased. Once octane was reached, the initial α and ∆ decreasing trend
9
10
11 was reversed and silicone oil was unable to cleanly slide off the coating because these liquids
12
13 had very low CAs. The extensive spreading of these liquids increased the base diameter w of
14
15 their droplets and eventually the effect of the elevated w prevailed over the decrease in and the
16
17
18 overall effect was for α and ∆ to increase as decreased.
19
20 As for the immiscible series, two factors could have contributed to the switching of the
21
22 order between the α values of diiodomethane and DMF. First and probably more importantly,
23
24
25 the room-temperature density of diiodomethane is 3.32 g/mL, which is much higher than the
26
27 corresponding value of 0.94 g/mL for DMF.46 At an equal droplet volume of 5 µL, the mass m
28
29
30
of the diiodomethane droplet was much larger. According to eq. 2, its α value should be smaller.
31
32 Second, the degree of PDMS layer swelling by the two solvents should differ. While the
33
34 Hildebrand solubility parameters are 14.9 and 24.6 (J/mL)1/2 for PDMS and DMF,44 respectively,
35
36
37
this value is 24.0 (J/mL)1/2 for diiodomethane.47 The smaller difference between the solubility
38
39 parameters of diiodomethane and PDMS suggests that diiodomethane should swell PDMS to a
40
41 greater degree than DMF, thus imparting diiodomethane with better sliding performance than
42
43
DMF.
44
45
46 For two liquids (e.g., methanol vs. decane) that have a similar value but are immiscible
47
48 and miscible with PDMS, respectively, the PDMS-incompatible liquid had higher α and ∆
49
50
51
values. This difference has been previously attributed to the different solvation states of the
52
53 surface-grafted PDMS chains under the two types of test liquids.30 Under decane, the grafted
54
55 PDMS chains became swollen. Consequently, the swollen and less viscous PDMS layer
56
57
58 15
59
1
2
3 acquired more liquid-like behavior and thus offered better test liquid sliding properties (Scheme
4
5
6 1c vs. Scheme 1d).
7
8 Effect of Varying the Molecular Weight of PDMS. The trends regarding the CA, α, and
9
10
∆ variation with the molecular weight of PDMS were also interesting. Due to the low CA, α,
11
12
13 and ∆ values measured for the PDMS-compatible liquids and the relatively large errors in their
14
15 measurements, drawing unambiguous conclusions about the variation trends for this series of
16
17
18 liquids was challenging. However, the data involving the PDMS-incompatible liquids did
19
20 exhibit clear trends. The P1-g-PDMS5k-based coating featured the lowest α and ∆ values for all
21
22 test liquids and the highest CA values for all of the liquids except diiodomethane.
23
24
25 To confirm the trends extracted from Table 1, CA, α, and ∆θ values of water,
26
27 diiodomethane, and hexadecane were measured on coatings containing 2.00% (m/m) PDMS of
28
29 different molecular weights (Table 2). As was seen with the 6.0% (m/m) coatings, varying the
30
31
32 molecular weight of PDMS did not significantly change the CA, α, or ∆θ values of hexadecane.
33
34 In contrast, the α and ∆θ values of water increased from 18 ± 2° and 5 ± 4° on the PDMS5k-
35
36
37 based coating to 32 ± 3° and 11 ± 2° on the PDMS1k-containing coating and then to 40 ± 3° and
38
39 16 ± 4° on the PDMS10k-based coating. Meanwhile, diiodomethane slid equally well, within
40
41 experimental errors, on the PDMS5k- and PDMS1k-based coatings but less readily on the
42
43
PDMS10k-based coating.
44
45
46
47 Table 2. Effect of varying the molecular weight of PDMS on the CA, α, and ∆θ values of three
48 test liquids on coatings containing 2.00% (m/m) PDMS.
49
Test CA (o) α (o) ∆θ (o)
50 Liquid PDMS1k PDMS5k PDMS10K PDMS1k PDMS5k PDMS10K PDMS1k PDMS5k PDMS10K
51 Water 104 ± 2 106 ± 2 104 ± 2 32 ± 3 18 ± 2 40 ± 3 11 ± 2 5±4 16 ± 4
52 Diiodomethane 71 ± 2 73 ± 2 75 ± 1 7±2 8±1 21 ± 1 10 ± 2 9±2 20 ± 2
53 Hexadecane 34 ± 2 31 ± 3 34 ± 1 6±1 6±1 7±1 3±1 3±1 2±1
54
55
56
57
58 16
59
1
2
3 Given the fact that at least eight or nine measurements were made to yield each reported CA
4
5
6 value in Table 1, the difference between the CA values of 107 ± 1° for PDMS5k-based coating
7
8 and 105 ± 1° for PDMS1k- and PDMS10k-based coatings should be statistically meaningful. As
9
10 was discussed above, these values could be employed to calculate the percentile areas of water-
11
12
13
contacting PU using eq. 1. This exercise yielded water-contacting PU percentile areas of 4 ± 4%
14
15 and 12 ± 5% for the PDMS5k-containing coating and the other two coatings, respectively. Thus,
16
17 a possible explanation for the lower α and ∆θ values obtained with the PDMS5k-based coatings
18
19
20 was that the PU surface was better protected by the PDMS5k side chains than by the other PDMS
21
22 side chains during exposure to water or the other incompatible liquids.
23
24 We note that the equilibrium water CA of 105.3° reported in Figure 3 was smaller than
25
26
107 ± 1° reported in Table 1 for water on the PDMS5k-based coating. This smaller CA value
27
28
29 could be due to the larger water droplet of 15 µL employed in the former case rather than the
30
31 smaller droplet of 5 µL employed in the latter scenario. The larger droplet, if assumed to take up
32
33 the shape of a perfect sphere, would have a diameter of 3.1 mm. On the other hand, the capillary
34
35
36 length is 2.7 mm for water at room temperature as calculated from (γ/ρg)1/2, where γ, ρ, g are the
37
38 surface tension of water, the density of water, and gravitational acceleration, respectively.48 The
39
40
higher diameter of the droplet than the capillary length suggests that this droplet could sag due to
41
42
43 the overcome of the surface tension force by the gravitational force. Aside from this likely
44
45 reason, the measured CA value changed from drop to drop for the same liquid within
46
47 experimental errors even for droplets of the same size.
48
49
50 The extent of protection offered by PDMS should depend on the thickness of the PDMS
51
52 layer as well as the grafting density of the surface PDMS chains. Referring to Schemes 2b and
53
54 2d, one realizes that the establishment of a water and PU interface requires water to fill a
55
56
57
58 17
59
1
2
3 transient and constantly-deforming nanochannel in the liquid-like PDMS layer and thus the
4
5
6 creation of unfavorable water/channel wall contact points. Evidently, a thinner PDMS layer
7
8 would bear shallower nanochannels and fewer PDMS/water contact points would be required to
9
10 create these nanochannels. Thus, it may be energetically more favorable to create pinholes
11
12
13
through a thinner PDMS layer and such a layer may offer less protection to the underlying PU
14
15 matrix. Of course, the energy required to create a pinhole also depends on the density of the
16
17 surface PDMS chains. A higher chain density under otherwise identical conditions decreases the
18
19
likelihood of pinhole formation and thus provides a greater degree of surface protection.
20
21
22 The α and ∆θ values of the PDMS-incompatible liquids were higher on the PDMS1k-based
23
24 coatings than on the PDMS5k-based coatings, and this can be attributed to the small thickness of
25
26
the PDMS1k layer. In this case, the PDMS layer could not be thicker than ~ 4.0 nm, the length of
27
28
29 a fully stretched PDMS1k chain. The dry PDMS layer (Scheme 1b) should be thinner than 4.0
30
31 nm not only because of the collapsing of the PDMS chains in the dry state but also because of
32
33 the increased probability for the partial embedment of the PDMS chains within the PU matrix.
34
35
36 Since the incompatibility between two polymers typically decreases as the molecular weight of
37
38 one polymer is decreased, the shortest PDMS1k chain should exhibit the highest compatibility
39
40 with the PU matrix, thus making it the most likely of the three PDMS lengths to be partially
41
42
43 embedded in the PU matrix. A possibly thinner surface PDMS layer on the PDMS1k-containing
44
45 coatings gave rise to the higher α and ∆θ values of the PDMS-incompatible liquids.
46
47 A lower surface density for the PDMS10k chains might be the culprit for its weaker de-
48
49
50 wetting properties than the PDMS5k layer. The PDMS surface density is a complex function of
51
52 kinetic and thermodynamic factors. On the kinetic front, the extent of P1-g-PDMS stratification
53
54 is postulated to depend on the rupture rate of the P1-g-PDMS micelles on the coating’s surface
55
56
57
58 18
59
1
2
3 during coating formation, the migration rate of the P1-g-PDMS chains in the sub-surface layers
4
5
6 to the surface, and the rate of matrix curing. In terms of thermodynamic, the “equilibrium”
7
8 surface density of the P1-g-PDMS chains is postulated to be governed by a balance between the
9
10 system’s surface energy reduction due to PDMS stratification and reductions in the translational
11
12
13
entropy of the stratified P1-g-PDMS chains and in the configurational entropy of the PDMS
14
15 chains.49 Indeed, a surface stratification equilibrium would probably not be established because
16
17 of the concurrent coating curing process. If the thermodynamic argument can be used at all, the
18
19
“equilibrium” surface density of the PDMS10k chains would be lower than that of the PDMS5k
20
21
22 chains because the molar concentration of PDMS10k in the final coating containing 6.0% (m/m)
23
24 of PDMS10k would be lower than that of the PDMS5k chains and the entropy cost associated with
25
26 maintaining the same surface density for the PDMS10k chains would be higher than that for the
27
28
29 PDMS5k chains. We further note that PDMS10k stratification would be kinetically slower than
30
31 that for PDMS5k stratification. Thus, it is possible that PDMS5k formed a denser surface layer
32
33 than PDMS10k due to both thermodynamic and kinetic considerations. At a presumably lower
34
35
36
surface density, PDMS10k would perforate more readily during exposure to water and this coating
37
38 could consequently exhibit worse sliding properties for PDMS-incompatible liquids than what is
39
40 offered by the PDMS5k-containing coating.
41
42
An alternative explanation could have been offered for the decrease in the sliding properties
43
44
45 of PDMS-incompatible liquids as the molecular weight of PDMS increased from 5.0 to 10.0
46
47 kDa. Hozumi and coworkers grafted monolayers of PDMS chains with molecular weights
48
49
between 6 and 100 kDa onto silicon wafers and discovered that the α and ∆θ values increased as
50
51
52 the molecular weight of PDMS increased.23 Their explanation was that the viscosity in the
53
54 grafted layer increased and the configurational entropy of the grafted chains decreased as the
55
56
57
58 19
59
1
2
3 molecular weight of the grafted polymer increased. While the viscosity increase of a polymer
4
5
6 melt with the molecular weight of the polymer is well known, the configurational entropy of the
7
8 grafted chains could go up because longer chains in a polymer brush could be more squeezed
9
10 than the shorter chains.49-50 The increase in the viscosity and the decrease in the configurational
11
12
13
entropy both decreased the liquid-like nature of the grafted PDMS layer and could have caused
14
15 the increases in the α and ∆θ values. This deterioration in the liquid sliding properties with
16
17 increasing PDMS molecular weight was also reported by Varanasi, who investigated how the
18
19
20 liquid sliding properties of SLIPS coatings varied when the viscosity of the pore-filling silicone
21
22 oil was changed.19
23
24 XPS Data. An XPS study was performed to determine the atomic abundances of Si in the
25
26
three coatings. The analysis utilized an electron take-off angle of 90° and an X-ray incident
27
28
29 angle of 54.7°, which corresponded to a XPS probing depth of ~ 6 nm.51 These settings yielded
30
31 the silicon atomic abundances of 12.5%, 12.2%, and 15.9% for the coatings containing PDMS1k,
32
33 PDMS5k, and PDMS10k, respectively. These experimental values were all much higher than the
34
35
36 calculated bulk silicon atomic content of 1.4% for coatings containing 6.0% (m/m) of PDMS.
37
38 Thus, the results suggested that PDMS stratified to the surface in every case.
39
40 However, the Si abundance values were still lower than 25%, a value that would be
41
42
43 expected for a pure PDMS layer that was thicker than ~ 6 nm, the probing depth of XPS. Since
44
45 our new coating surface model of Scheme 1b assumes that the surface PDMS has two layers: a
46
47 dent-bearing but essentially pure PDMS layer and a PU layer encapsulating the PDMS chain
48
49
ends, the lower Si content values suggest that the pure PDMS layer at the top was thinner than ~
50
51
52 6 nm. Aside from this, we could not deduce, from the Si abundance values, the thickness of the
53
54
55
56
57
58 20
59
1
2
3 upper dent-bearing PDMS layer because we did not know the contributions made by the buried
4
5
6 parts of the PDMS chains towards the determined Si contents.
7
8 Ink Resistance. The coatings containing 6.0% (m/m) of PDMS with different molecular
9
10 weights were also subjected to an ink resistance test. In such a test, a Sharpie King Size
11
12
13
permanent marker was drawn across each coating. Figure 4 compares the still images taken from
14
15 videos that recorded what occurred 2 s after the marker strokes were made and when the
16
17 shrinkage of the ink trace had stopped. While the marker left a uniform trace on an uncoated
18
19
glass plate, the ink traces contracted on the three coatings containing PDMS side chains with
20
21
22 different molecular weights. Moreover, the contracted ink traces could be easily wiped away
23
24 from the coated surfaces with a Kimwipe® tissue. In contrast, the uniform trace left on the
25
26 uncoated glass plate could not be removed in this manner. Thus, the ink and possibly other
27
28
29 liquid-borne contaminants did not readily spread on the tested NP-GLIDE formulations.
30
31 Moreover, a contracted contaminant trace was more easily removed from the coatings than from
32
33 the uncoated glass.
34
35
36
The contraction of the ink traces on the NP-GLIDE coatings should not be surprising, as
37
38 these coatings featured the low- liquid-like PDMS chains on their surfaces. On the other hand,
39
40 the solvents used to formulate the ink included alcohols and glycol ethers,52 which all have
41
42
43
values higher than those of PDMS. The ink traces contracted to expose the low- PDMS, thus
44
45 decreasing the system’s overall surface energy. The contraction was kinetically feasible because
46
47 of the liquid-like nature of the PDMS layer.
48
49
50
51
52
53
54
55
56
57
58 21
59
1
2
3
4 a i ii iii iv
5
6
7
8
9
10
11 b
12
13
14
15
16
17
18 Figure 4. Anti-marker test results for coatings containing 6.0% (m/m) PDMS. While row (a) shows the
19 marker trace after its application, the status of the coatings after the removal of the marker trace
20
with a Kimwipe® tissue is shown in row (b). Columns (i), (ii), (iii), and (iv) display photos
21
of samples that contained no coating and those that were coated with PU containing
22
23
P1-g-PDMS1k, P1-g-PDMS5k, and P1-g-PDMS10k, respectively. The gray
24 rectangular stripe in the photo arises from a double-sided adhesive
25 tape used to glue the glass plates to a piece of paper.
26
27
28 Fine differences were noticed regarding the performance of the three formulations. On the
29
30 PDMS5k-containing coating, the ink trace eventually contracted into tiny patches. Narrow ink
31
32
33 stripes and some overlapping stripes were seen on the PDMS1k-based coatings and many
34
35 overlapping ink stripes were visible on the PDMS10k-based coatings. Thus, the PDMS5k-based
36
37 coating had the best ink contraction performance, which was consistent with their better CA, α,
38
39
40 and ∆θ values for various test liquids.
41
42 The ink contraction patterns were also analyzed quantitatively. In such an experiment,
43
44
parallel strokes that contacted one another but did not overlap were drawn across an entire slide and a
45
46
47 photo was then taken of the contracted pattern. The photo was converted into a grayscale image
48
49 and the threshold was adjusted to create a black and white image with only the contracted ink
50
51 droplets appearing in black. The particle analysis function of the ImageJ software was
52
53
54 subsequently used to count the number and size of the ink droplets in a 1.00 × 1.00 cm2 area near
55
56 the centre of the original slide. The total area of the coating covered by ink was then calculated.
57
58 22
59
1
2
3 The P1-g-PDMS1k, P1-g-PDMS5k, and P1-g-PDMS10k coatings containing 6.0% (m/m) PDMS
4
5
6 had total ink areas of 8.3, 5.6 ± 0.8, and 8.1 mm2, respectively, corresponding to final percentile
7
8 ink areas of 8.3%, 5.6 ± 0.8%, and 8.1%. Here the experiments were only repeated four times
9
10 for the PDMS5k-containing sample and the values 5.6 mm2 and 0.8 mm2 thus represented the
11
12
13
average final ink area obtained from the four trials and the standard deviation of this average
14
15 value, respectively. Since the magnitude of the errors should be similar for the other two
16
17 samples, the difference between 5.6 ± 0.8% and the other two values were statistically
18
19
significant, thus confirming that the P1-g-PDMS5k coating was the most effective at contracting
20
21
22 ink.
23
24 The writing and erasing test was repeated on each coating at least 20 times and no
25
26 degradation in the shrinking behavior was detected visually by the end of this experiment. A
27
28
29 more quantitative analysis involved measuring the transmittance values of the different coatings
30
31 at 500 nm after the writing and erasing test. Using an uncoated glass slide as a reference or
32
33 assuming a transmittance value of 100% for the reference, we measured a transmittance of
34
35
36
99.8% for a pristine coating containing 6.0% (m/m) of PDMS5k. After the marker strokes had
37
38 been applied on the reference and sample once, the applied ink was allowed to dry, and the
39
40 surface was subsequently wiped with a Kimwipe under similar conditions, the transmittances of
41
42
the reference and sample were found to be 5.8% and 99.8%, respectively, thus confirming the
43
44
45 facile removal of the ink trace from the coated surface. After 5 and 10 writing-erasing cycles,
46
47 the transmittances of the coated glass plate were still high at 99.8% and 99.6%, respectively.
48
49 Thus, the PDMS5k-containing coating was highly durable.
50
51
52 Paint Contraction. The different coatings were also tested for their abilities to contract
53
54 ColorMaster Krylon Banner Red spray paint that contained a mixture of acetone, toluene,
55
56
57
58 23
59
1
2
3 propane, butane, ethyl-3-ethoxypropionate, and dimethyl carbonate as the solvent. Figure 5
4
5
6 compares the still images taken from videos that were recorded after the application of the paint
7
8 onto PU coatings that were placed vertically. While the uncoated glass slide did not contract
9
10 paint, the fastest paint contraction was observed on the P1-g-PDMS5k-based coating. By 35 s
11
12
13
when the paint had stopped contracting further, the highest extent of paint contraction was also
14
15 achieved by the P1-g-PDMS5k-based coating.
16
17
18
19
20 i ii iii iv
21
22
23
24
25
26 0 seconds
27
28
29
30
31
32
33
34
35 5 seconds
36
37
38
39
40
41
42
43
44 35 seconds
45 Figure 5. Photos showing the status of coating surfaces after the spraying of a red paint onto samples
46 containing (i) no coating, or 6.0% (m/m) of (ii) PDMS1k, (iii) PDMS5k, and (iv) PDMS10k, respectively.
47
48
49
50 Effect of Varying the PDMS Content. The effect of varying the PDMS5k content on the
51
52 performance of the coating was also investigated. For this purpose, the CA, α, and ∆θ values of
53
54
water, diiodomethane, and hexadecane were measured on coatings containing 0.50, 1.00, 2.00,
55
56
57
58 24
59
1
2
3 and 6.0% (m/m) of PDMS5k. While the data for the latter two samples are listed in Tables 1 and
4
5
6 2, Table 3 shows the data obtained for the coatings containing 0.50 and 1.00% (m/m) of PDMS5k.
7
8
9 Table 3. CA, α, and ∆θ values for P1-g-PDMS5k-based coatings
10
11
containing 0.50 and 1.00% (m/m) of PDMS.
12 Test CA (°) α (°) ∆θ (°)
13 Liquid 0.50% (m/m) 1.00% (m/m) 0.50% (m/m) 1.00% (m/m) 0.50% (m/m) 1.00% (m/m)
14 Water 99 ± 2 106 ± 2 54 ± 2 21 ± 3 12 ± 9 6±3
15 Diiodomane 53 ± 3 72 ± 1 13 ± 3 7±1 18 ± 2 9±2
16 Hexadeane. 16 ± 1 29 ± 1 11 ± 2 8±1 6±1 3±1
17
18
19
20 The CA, α, and ∆θ values on coatings containing 2.00 and 6.0% (m/m) of PDMS5k were
21
22 identical within experimental error. Minor and substantial changes in these values were
23
24 observed when the PDMS5k content was decreased to 1.00 and 0.50% (m/m), respectively. For
25
26
27 example, the α values observed for 15 µL water droplets were 17 ± 2°, 18 ± 2°, and 21 ± 3° at
28
29 the PDMS5k contents of 6.0, 2.00, and 1.00% (m/m), respectively. At 0.50% (m/m) of PDMS5k,
30
31 the α observed with 15 µL water droplets was 54 ± 2°.
32
33
34 The insignificant variation of the CA, α, and ∆θ values of the coatings with the PDMS5k
35
36 contents above 1.00% (m/m) was reasonable because the low-surface-tension PDMS5k stratified
37
38
toward the coating surface and many past studies have established that the approach of the
39
40
41 asymptotic de-wetting properties of such systems containing PDMS was established at very low
42
43 concentrations of the stratifying agent.53-54
44
45 The fact that the limiting de-wetting performance was reached at the low bulk PDMS5k
46
47
48 concentrations of 1.00 or 2.00% (m/m) has important practical implications. Mono-
49
50 functionalized PDMS is more expensive than the other components of a PU coating. Its use at a
51
52 very low concentration ensures that the NP-GLIDE coatings would be economically viable and
53
54
55
thus suitable for a wide range of applications.
56
57
58 25
59
1
2
3 The coatings containing various amounts of PDMS5k were further subjected to the ink
4
5
6 contracting and erasing test and a set of results are shown in Figure 6. Increasing the PDMS5k
7
8 content from 1.00 to 6.0% (m/m) appeared to only slightly improve the ink contraction
9
10 performance of the coating. Using the ImageJ software to quantify the total areas occupied by
11
12
13
the contracted ink after its initial application onto the surface of each slide yielded the final ink
14
15 percentile areas of 6.8%, 6.0%, and 5.6% on coatings containing 1.00, 2.00, and 6.0% (m/m) of
16
17 PDMS, respectively, which was consistent with the results obtained via visual inspection. In
18
19
20
further agreement with the trends in the variation of CA, α, and ∆θ, a sudden deterioration in the
21
22 coating’s ink contraction performance was observed when the PDMS5k content was decreased to
23
24 0.50% (m/m). On this coating, the ink trace did not contract at all.
25
26
27 a i ii iii iv
28
29
30
31
32
33
34
35
36
37 b
38
39
40
41
42
43
44 Figure 6. Anti-smudge test results for P1-g-PDMS5k-based coatings that contained (i) 0.50, (ii) 1.00, (iii)
45
2.00, and (iv) 6.0% (m/m) of PDMS, respectively. The images shown were recorded (a) after ink had
46
47 been applied and allowed to contract and (b) subsequently after the surfaces had been cleaned
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1
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3 with a Kimwipe® tissue. The gray rectangular stripe in the photo arises from a double-sided
4 adhesive tape used to glue the glass plates to a piece of paper.
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Figure 6b shows the status of the different coatings after their cleaning with Kimwipe®
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10 tissues. Ink could be cleanly and fully removed from coatings that contracted the ink in the first
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12 place but could not be removed from the coating containing only 0.50% (m/m) of PDMS5k.
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14
Figure 7 compares the still images taken from videos that were recorded after the
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16
17 application of the red paint onto the PU coatings containing various weight fractions of PDMS5k.
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19 The paint contracting capabilities of coatings with 2.00 and 6.0% (m/m) of PDMS5k were
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21 essentially identical. The paint seemed to contract more gradually on the coating containing
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24 1.00% (m/m) of PDMS5k. Additionally, more paint seemed to remain on this coating at 30 s
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26 when paint had stopped shrinking further. In contrast with the other coatings, the coating
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28 containing 0.50% (m/m) of PDMS5k did not exhibit ink contraction capability.
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31 i ii iii iv
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36 0 seconds
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43 5 seconds
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49 30 seconds
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51 Figure 7. Photos showing the conditions of coating surfaces after the spraying of a red paint onto P1-g-
52 PDMS5k-based coatings containing (i) 0.50, (ii) 1.00, (iii) 2.00,
53 and (iv) 6.0% (m/m) of PDMS, respectively.
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58 27
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3 III. Conclusions
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6 Grafting PDMS chains with molecular weights of 1.0, 5.0, and 10.0 kDa to a polyol P1
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8 backbone yielded graft copolymers P1-g-PDMS. These graft copolymers were used to prepare
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10 NP-GLIDE PU coatings containing 2.00 and 6.0% (m/m) PDMS. At a given PDMS content of
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2.00 or 6.0% (m/m), the de-wetting properties of the coatings were the best when P1-g-PDMS5k
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15 was used as the de-wetting enabler. This performance was reflected by the lower α and ∆θ
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17 values measured for water and other PDMS-incompatible test liquids on the PDMS5k-based
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20 coatings in comparison with those observed on the PDMS1k- and PDMS10k-based coatings. In
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22 addition, traces of a commercial ink and a sprayed red paint contracted the fastest and most
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24 extensively on these coatings.
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A new model has been proposed describing the packing of PDMS chains on the surface of
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29 NP-GLIDE coatings. The model assumes the formation of a defective PDMS monolayer on the
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31 coating surface. Dents in this monolayer are assumed to occur at locations where the grafting
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33 densities of the PDMS chains are the lowest and these dents may evolve into pinholes when a
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36 coating is immersed into water or other PDMS-incompatible liquids. A higher number of
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38 contact points between a test liquid and the PU components likely accounts for the deterioration
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40 in the de-wetting performance of a coating. Based on this model, the low thickness of the
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43 surface PDMS1k layer has been suggested as a probable reason for the worse performance
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45 exhibited by the PDMS1k-based coatings in comparison with the PDMS5k-based coatings. On the
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47 other hand, the large spacing between the surface PDMS10k chains and the higher population for
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49
surface dents in the upper PDMS10k layer likely accounts for the worse performance of the
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52 PDMS10k-based coatings than the PDMS5k-based coatings. This model provides valuable insight
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58 28
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1
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3 that will enable the design of new generations of enhanced coatings with numerous practical
4
5
6 applications.
7
8 The de-wetting properties of P1-g-PDMS5k coatings containing 0.50, 1.00, 2.00, and 6.0%
9
10 (m/m) PDMS have also been compared. Test liquids readily slid off these coatings containing
11
12
13
1.00% (m/m) PDMS or more, while ink traces and paint films readily contracted on these
14
15 surfaces. Increasing the PDMS content to 6.0% (m/m) only marginally improved the de-wetting
16
17 properties. When the PDMS content was decreased to 0.50% (m/m), the contact angles of
18
19
various test liquids were notably lower, and the sliding angles and contact angle hysteresis were
20
21
22 greatly increased. Furthermore, the 0.50% (m/m) PDMS coatings were unable to induce the
23
24 shrinkage of ink or paint and the deposited ink traces could not be wiped clean. The poor
25
26 performance of the coating containing 0.50% (m/m) PDMS5k was likely due to the low density of
27
28
29 the surface-stratified PDMS chains and high density of defects in this layer. The fact that only
30
31 1.00% (m/m) of PDMS was required to enable robust NP-GLIDE coatings demonstrates the
32
33 practical value of this technology and ensures the affordability of these coatings for various
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35
36
applications.
37
38
39
40 Supporting Information
41
42 The Supporting Information is available free of charge on the ACS Publication website at DOI:
43
44
Experimental section, discussion of polymer synthesis and characterization, coating
45 formation, and cross-sectional AFM images of the coatings.
46
47
48
49 AUTHOR INFORMATION
50
51
52 Corresponding author
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54
55
E-mail: gliu@chem.queensu.ca (G.L.)
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58 29
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1
2
3 ORCID
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5
6 Guojun Liu: 0000-0002-9643-5070
7
8
9 Notes
10
11
12 The authors declare no competing financial interest.
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14
15 Acknowledgment. NSERC of Canada and Lorama are thanked for sponsoring this research.
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17
18
GL thanks the Government of Canada for a Canada Research Chair position in Materials Science.
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9 TOC Graphic
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