polymers Article
Increased Surface Roughness in Polydimethylsiloxane Films by Physical and Chemical Methods Jorge Nicolás Cabrera 1,2 , Mariano M. Ruiz 1 , Mirta Fascio 3,4 , Norma D’Accorso 3,4 , Rosica Mincheva 5 , Philippe Dubois 5 , Leonardo Lizarraga 6, * and R. Martín Negri 1,2, * 1 2 3 4 5 6
*
Instituto de Química Física de Materiales, Ambiente y Energía (INQUIMAE), Ciudad Autónoma de Buenos Aires C1428EGA, Argentina;
[email protected] (J.N.C.);
[email protected] (M.M.R.) Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires (UBA), Ciudad Autónoma de Buenos Aires C1428EGA, Argentina Centro de Investigación en Hidratos de Carbono (CIHIDECAR-CONICET), Ciudad Autónoma de Buenos Aires C1428EGA, Argentina;
[email protected] (M.F.);
[email protected] (N.D.) Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, UBA, Ciudad Autónoma de Buenos Aires C1428EGA, Argentina Center of Innovation and Research in Materials & Polymers (CIRMAP), University of Mons, 7000 Mons, Belgium;
[email protected] (R.M.);
[email protected] (P.D.) Centro de Investigaciones en Bionanociencias (CIBION-CONICET), Godoy Cruz 2390, 1st Floor, Ciudad Autónoma de Buenos Aires C1425FQD, Argentina Correspondence:
[email protected] (L.L.);
[email protected] (R.M.N.); Tel.: +54-114-899-5500 (ext: 5596) (L.L.); +54-114-576-3378 (R.M.N.)
Received: 15 June 2017; Accepted: 25 July 2017; Published: 2 August 2017
Abstract: Two methods, the first physical and the other chemical, were investigated to modify the surface roughness of polydimethylsiloxane (PDMS) films. The physical method consisted of dispersing multi-walled carbon nanotubes (MWCNTs) and magnetic cobalt ferrites (CoFe2 O4 ) prior to thermal cross-linking, and curing the composite system in the presence of a uniform magnetic field H. The chemical method was based on exposing the films to bromine vapours and then UV-irradiating. The characterizing techniques included scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM) and magnetic force microscopy (MFM). The surface roughness was quantitatively analyzed by AFM. In the physical method, the random dispersion of MWCNTs (1% w/w) and magnetic nanoparticles (2% w/w) generated a roughness increase of about 200% (with respect to PDMS films without any treatment), but that change was 400% for films cured in the presence of H perpendicular to the surface. SEM, AFM and MFM showed that the magnetic particles always remained attached to the carbon nanotubes, and the effect on the roughness was interpreted as being due to a rupture of dispersion randomness and a possible induction of structuring in the direction of H. In the chemical method, the increase in roughness was even greater (1000%). Wells were generated with surface areas that were close to 100 µm2 and depths of up to 500 nm. The observations of AFM images and FTIR spectra were in agreement with the hypothesis of etching by Br radicals generated by UV on the polymer chains. Both methods induced important changes in the surface roughness (the chemical method generated the greatest changes due to the formation of surface wells), which are of great importance in superficial technological processes. Keywords: composites; roughness; magnetism; bromine
Polymers 2017, 9, 331; doi:10.3390/polym9080331
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1. Introduction The modification of polymer surfaces finds applications in many relevant areas, such as the development of super-hydrophobic membranes for oil–water separation [1,2], activation surfaces for microfluidics [3], the attachment of biomolecules for biosensors [4], self-replenishing coatings [5], and anti-bacterial and fouling release coatings [6–8]. Such modification to increase the surface roughness is a topic of permanent interest, as it may favor or disfavor the adsorption of macromolecules or the formation of biofilms on the polymer surface. In fact, the motivation for the present work is related to the interesting antifouling properties of polydimethylsiloxane (PDMS) surfaces and the possibilities to change these by modifying the roughness. The low surface energy of silicone materials makes them useful in the production of non-sticking and/or readily cleanable coatings in aqueous environments [9]. However, despite the inherently good antifouling properties of silicones, the PDMS-based coatings have a limited practical use because they are mechanically weak and easily damaged. Some of the authors have reported that the incorporation of very low amounts (0.5% w/w) of multi-walled carbon nanotubes (MWCNTs) into the silicone matrix spectacularly improves the physical and rheological behavior of the PDMS resin [10]. This was found to trigger significant changes in the nanocomposite surface topography, concomitant with variations in the wettability behavior upon immersion in water. This restructuring of the surface allows for an enhancing of the fouling-release performance of the coatings towards two major fouling species, the green macroalga (seaweed), Ulva linza, and the barnacle, Balanus amphitrite [11]. The obtained results suggest that, independently of the bulk mechanical performances, the surface properties significantly affect the fouling-release behavior of the filled materials. A great variety of methods have been reported to increase surface roughness, including UV reactions [12], UV grafting [13,14], UV/ozone reactions [15,16], laser/plasma etching [17,18], chemical surface treatments [19], sequential growth of polymer layers [20–22], surface casting [7], and nanofiller loading [23–26]. All mentioned procedures present relative advantages and drawbacks. For instance, UV/ozone methods currently require two spectral lines, the first to produce ozone and the other to generate oxygen from ozone; oxygen plasma methods introduce high-energy ions and radicals, which render several coupled oxidations; UV grafting currently requires the adsorption of a photo-initiator; etc. [27]. Therefore, the search for simple new methods to increase the surface roughness of polymers continues. We note that the wide variety of methods can be classified in two large groups. One group contains those methods for which the roughness is increased because the polymer structure is chemically modified. These methods are highly reactive towards the polymer matrix, typically due to using UV reactions, as mentioned previously. The other group is formed by those methods that do not produce a chemical attack of the polymer—mainly those based on incorporating nanofillers in the matrix. For instance, it has been reported that the fine random dispersion of MWCNTs in PDMS, forming PDMS/MWCNT composites, increases the surface roughness [28]. An interesting alternative not explored in the literature as a method of inducing roughness, as far as we know, is to prepare structured composites for which nanofillers are preferentially oriented in a direction perpendicular to the surface. Our group has extensive experience with preparing structured composites using magnetic nanofillers, such as cobalt ferrites (CoFe2 O4 ), which are oriented by magnetic fields applied during curing or solvent evaporation [29–38]. These works suggest the possibility of increasing the roughness by preparing composites containing not only MWCNT, but also CoFe2 O4 magnetic nanoparticles, and curing the composite in the presence of a magnetic field perpendicular to the surface, generating structured PDMS/MWCNT/CoFe2 O4 composites. Therefore, the aim of the present work is to explore the possibilities of inducing a roughness increase in PDMS films by two approaches, each associated to a mentioned group of methods: (i) structured composite (PDMS/MWCNT/CoFe2 O4 ) curing in the presence of a magnetic field perpendicular to the surface; and (ii) surface attack through bromide radicals generated by UV reactions. The surface modifications induced using both methods were analyzed and then compared.
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2. Materials and Methods 2.1. Chemicals PDMS Sylgard 184 (from Dow Corning, Midland, MI, USA) was used as a silicone elastomer consisting of two parts, A and B, which needed to be mixed together in a ratio of 10:1 in order to obtain the cross-linked material via a hydrosilylation reaction. According to the supplier, the formulation contained an α,ω-vinyl-terminated poly(dimethylsiloxane) polymer (DP = 434), a poly(dimethylsiloxane-co-hydrogenomethylsiloxan) copolymer, a vinyl resin additive and a platinum-based catalyst. Bromine (Br2 ) blisters were obtained from Merck, Kenilworth, NJ, USA. MWCNTs were provided by Sigma Aldrich (St. Louis, MI, USA Code 6941855G; average length: 0.5–200 µm; average diameter: 7–15 nm). Na2 S2 O3 was provided by Anedra (Buenos Aires, Argentina). All solvents and reagents were of analytical quality and were used as received. The synthesis and characterization of cobalt ferrites (CoFe2 O4 ; 15 nm average diameter) of a high purity and crystallinity were reported in previous works [30,38]. Cover-slips for optical microscopy were used as glass substrates for preparing the films. The cover-slips were cleaned beforehand with acetone, ethanol and distilled water. A few films were prepared on an aluminium substrate (Sigma-Aldrich, St. Louis, MO, USA) under a similar cleaning procedure. 2.2. Preparation of PDMS/Filler Composite Films PDMS base and cross-linker agents were mixed in proportions of 10:1 (w/w) at room temperature. Typically, 2 g of the base/cross-linker agent was used. Then, toluene was added (1 mL) to aid mixing and to ensure faster air bubble removal. This mixture was left under magnetic stirring until most of the toluene had evaporated, to obtain a viscous fluid system with an adequate fluidity for preparing the films. Composites with nanofillers dispersed in PDMS were also prepared using MWCNTs, by adding different amounts of MWCNTs to a solution of PDMS in toluene, before curing. The nominal weight fraction of MWCNT was about 1% w/w (without considering the toluene). To prepare the films, the viscous suspension was deposited onto glass substrates by spin-coating at room temperature (SPIN-1200D MIDAS SYSTEM spin-coater, Daejeon, Korea); 10 s at 2000 rpm followed by 15 s at 4000 rpm). Then, the samples were placed into an oven at 110 ◦ C to evaporate the rest of the toluene and to cure the polymer (cross-linking process). Some samples were prepared using a different method. On the glass substrate, two adhesive tapes were glued, separated by a distance of 2–3 cm. In the region between the two tapes, the viscous suspension of PDMS/fillers was poured and then slowly spread using a spatula or a plastic ruler. This system was then cured thermally. In this way, films of the composite deposited on the substrate were obtained, with thicknesses close to that of the adhesive tapes (thickness of the tape: 130 µm). This method is referred to here as the tape method. As mentioned previously, a few samples were prepared via the two methods (spin-coating and tape methods) on an aluminium substrate, for comparison, following the described protocols. In some cases, CoFe2 O4 particles were also added simultaneously with the nanotubes (in these cases: MWCNT ≈ 1% w/w; CoFe2 O4 ≈ 2% w/w). Some of the samples containing CoFe2 O4 were cured at room temperature under the application of a uniform magnetic field in a direction perpendicular to the surface. To perform this, the films formed on the substrate were placed between two rare-earth permanent magnets (samarium-cobalt alloys; disk shaped; flat surfaces; 36 mm diameter) immediately after the spin-coating process. The system was left between the magnets at room temperature until the toluene had completely evaporated and the polymer had cured. The magnetic field between the two magnets was close to the surface of the films and was, at its center, about 0.36 T (measured with a Hall probe sensor, Allegro Probe Model 1302A, Worcester, MA, USA).
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At At least least four four replicates replicates were were prepared prepared for for each each of of the the systems; systems; that that is, is, every every time time aa specific specific experimental condition was changed (substrate, method of preparation, composition, experimental condition was changed (substrate, method of preparation, composition, etc.), etc.), at at least least four four replicates replicates were were prepared. prepared. 2.3. Exposition to to Br Br22 Vapours Vapours and and UV UV Reaction Reaction 2.3. Exposition The in in order to expose PDMS/MWCNT composite films to Br2 vapours, to be followed The set-up set-upused used order to expose PDMS/MWCNT composite films to Br2 vapours, to be by UV irradiation, is shown in prepared by prepared the methods described in followed by UV irradiation, is Figure shown1.inBriefly, Figurethe 1. samples Briefly, the samples by the methods the previous section, without removal from their substrate, were placed faced down into a 175 mL described in the previous section, without removal from their substrate, were placed faced down hermetic Immediately closingbefore the vessel, mL of liquid bromine wasbromine introduced into a 175vessel. mL hermetic vessel. before Immediately closing0.5the vessel, 0.5 mL of liquid was into its bottom using a Pasteur pipette. Once the vessel was closed, the bromine did not evaporate introduced into its bottom using a Pasteur pipette. Once the vessel was closed, the bromine did not completely, but a liquid–vapour equilibriumequilibrium was established the chamber. Thus, the Br2Thus, (gas) evaporate completely, but a liquid–vapour was inside established inside the chamber. pressure waspressure estimated to estimated be about 0.2–0.3 bar, which thewhich estimated pressure of bromine the Br2 (gas) was to be about 0.2–0.3isbar, is thevapour estimated vapour pressure ◦ C [39]. The films were in contact with these vapours for 30 min (the presence of reddish Br at 25 of bromine at 25 °C [39]. The films were in contact with these vapours for 30 min (the presence of2 vapours can be observed in Figure 1b). Afterwards, the films were removed from the vessel; some of reddish Br 2 vapours can be observed in Figure 1b). Afterwards, the films were removed from the the filmssome wereofexposed to UV radiation from a medium-pressure (5 W) placed 2 cm from vessel; the films were exposed to UV radiation from aHg-lamp medium-pressure Hg-lamp (5 the W) samples (Figure 1c) during a variable exposure time (30 min or 1, 2, 3 or 4 h). Then, the samples placed 2 cm from the samples (Figure 1c) during a variable exposure time (30 min or 1, 2, 3 or were 4 h). washed with Na2 S2were O3 and waterwith and Na placed in an oven for 30 min at 70 ◦ C to remove possible drops Then, the samples washed 2S2O3 and water and placed in an oven for 30 min at 70 °C to of Br2 (liquid) condensed films.condensed on the films. remove possible drops of on Br2the (liquid)
Figure 1. 1. (a) (a)Internal Internalview viewofof cover in which sample holders placed. (b) Container with Figure thethe cover in which sample holders werewere placed. (b) Container with liquid liquid bromine in equilibrium with its vapour. The samples were located upside down on the bromine in equilibrium with its vapour. The samples were located upside down on the lid; thus, lid; the thus, the films were inwith contact with vapours. bromine vapours. (c)was Theremoved lid was removed vessel and films were in contact bromine (c) The lid from the from vesselthe and samples samples were placedand face-up and UV-irradiated. were placed face-up UV-irradiated.
2.4. Instrumentation 2.4. Instrumentation The thicknesses thicknesses of the dried dried films films were were measured measured using using aa surface surface profilometer profilometer (Veeco, model The of the (Veeco, model Dektak 150, Plainview, NY, USA), whose instrumental details are described in a previous work Dektak 150, Plainview, NY, USA), whose instrumental details are described in a previous work [36]. [36]. The thickness thickness of of the the film, film, L, L, was was measured measured as as aa function function of of the the scanned scanned distance, distance, and and the the average average The values of of L, L, referred referred to to as as , , were values were calculated calculated within within aa defined defined scanning scanning distance distance range range (4000 (4000 μm, µm, depending on the sample) starting from at least 100 μm from the edge of the film. depending on the sample) starting from at least 100 µm from the edge of the film. −−1 1 ;; resolution Fourier transform transform infrared infrared(FTIR) (FTIR)spectra spectra(4000–400 (4000–400cm cm resolution44cm cm−−11)) were Fourier were acquired acquired with with Nicolet 8700 (Madison, WI, USA) equipment using a Smart Orbit ATR accessory (single horizontal Nicolet 8700 (Madison, WI, USA) equipment using a Smart Orbit ATR accessory (single horizontal reflection with with aa diamond diamond crystal) crystal) and and aa DTGS DTGS detector. detector. reflection The structure structureofofthe thedried dried composite films investigated by scanning electron microscopy The composite films waswas investigated by scanning electron microscopy (SEM) (SEM) using a field emission scanning electron microscope (FESEM; Zeiss Supra 40 Gemini, using a field emission scanning electron microscope (FESEM; Zeiss Supra 40 Gemini, Oberkochen, Oberkochen, Germany). Germany). Atomic force forcemicroscopy microscopy (AFM) magnetic microscopy [40] were images were Atomic (AFM) andand magnetic force force microscopy (MFM)(MFM) [40] images acquired acquired to characterize the surfaces’ topography and the magnetic surface properties of the to characterize the surfaces’ topography and the magnetic surface properties of the composites. composites. A Bruker8 Multimode SPM (Santa Barbara, USA) and NanoScope V Controller A Bruker Multimode SPM (Santa 8Barbara, CA, USA) and CA, NanoScope V Controller (Billerica, Santa (Billerica, Santa Barbara, CA, USA) were used. The image analyses were performed using Gwyddion version 2.46 (Brno, Czech Republic) and Nanoscope version 9.1 software (Santa Barbara, CA, USA).
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Barbara, CA, USA) were used. The image analyses were performed using Gwyddion version 2.46 (Brno, Czech Republic) and Nanoscope version 9.1 software (Santa Barbara, CA, USA). The AFM images were acquired in the intermittent mode using silicon tips with a spring constant of 1–5 Nm−1 and a resonance frequency in the range of 60–100 kHz. Areas of typically 50 µm × 50 µm were scanned. The MFM images were obtained in the lift mode, while tapping was used to record the magnetic signal using the phase-detection mode. Magnetic probes (Co/Cr; model MESP) provided by Bruker were employed to acquire the MFM images. The tips were magnetized before use. The lift height was set close to 100 nm, and the scan size was 10 µm × 10 µm. For each AFM (or MFM) image, a reference plane (mean plane) was defined, and a Z-axis, perpendicular to that plane, was considered, where Z = 0 was on the plane. Z-values were calculated from the images in a discrete manner, where Zj was defined as the height of the jth-pixel from the mean plane. That is, Z is a discrete stochastic variable. Positive Z-values are associated to protrusions above the mean plane, while negative Z-values, to depressions below the plane. The average surface roughness (Ra ) of each AFM image was determined as the average deviation of height values from the N mean plane, when considering N pixels in a given image: Ra = N1 ∑ Zj (N = 262,144). For each sample, j =1
three AFM images (taken at different regions on the sample surface) were recorded. Considering that 4 replicated samples were prepared and analyzed, then the reported Ra values for each type of sample consisted of an average value and a standard deviation over 12 determinations. Other related roughness stochastic variables are usually considered, such as the “well depth” and heights profile. The well depth is the maximum variable value calculated as |Zj | when considering only the negative Zj , that is, those associated to each well (below the mean plane). Then the mean well depth and the associated standard deviation can be calculated, analogously to the calculation of Ra (but N, in this case, is equal to the number of wells). Finally, when the height values Zj are taken on a defined (arbitrary) line in the plane, they are usually referred to as height profiles on a line, and are plotted against the position on the defined line. 3. Results and Discussion No influence of the substrate used for depositing the films (glass and aluminium) and for the preparation method (spin-coating and tape methods) was observed. The results described here were independent of the substrate and preparation method. 3.1. Surface Roughness in PDMS/Filler Composites The thickness of all samples prepared by spin-coating was in the range of 20–40 µm, and was typically 30 µm. The samples prepared by the tape method (described in Section 2.2) had thicknesses of about 150 µm, which was close to the thickness of the tape. The presence of MWCNTs was detected in PDMS/MWCNT films by optical microscopy (Figure 2) and SEM (Figure 3). Moreover, the changes in surface features are clearly illustrated in the photographs of Figure 2 (taken with an optical microscope). It can be seen (qualitatively) in Figure 2 that the roughness increased when progressing in the series from PDMS to PDMS/MWCNT/CoFe2 O4 to PDMS/MWCNT/CoFe2 O4 + H (cured in the presence of the magnetic field H).
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Figure 2. 2. Optical Optical microscopies: microscopies: (a) (a)PDMS. PDMS. (b) (b) PDMS PDMS ++ MWCNT MWCNT (1%) (1%) ++ Fe Fe22CoO CoO4 4(2%). (2%).(c) (c)PDMS PDMS++ Figure Figure 2. Optical microscopies: (a) PDMS. (b) PDMS + MWCNT (1%) + Fe2CoO4 (2%). (c) PDMS + MWCNT(1%) (1%)++Fe Fe2CoO 4 (2%) ++ H.H. MWCNT 2 CoO 4 (2%) MWCNT (1%) + Fe2CoO4 (2%) + H.
In order to obtain SEM images with resolution, asas forfor those observed in in Figure 3, a3, In withan anacceptable acceptable resolution, those observed Figure Inorder orderto to obtain obtain SEM SEM images images with an acceptable resolution, as for those observed in Figure 3, a 10 kVkV electron source was used source (that is, electrons with higher a10 10 electron source was usedinstead insteadofof ofthe thecommon common3 33kV kV kV electron source was used instead the common kV source source (that (that is, is, electrons electrons with withhigher higher energy were used). This suggested that the the nanomaterials(MWCNT (MWCNTand andCoFe CoFe2 O 2O4)) were werecovered coveredby bya energy energywere wereused). used).This Thissuggested suggestedthat that thenanomaterials nanomaterials (MWCNT and CoFe 24O4) were covered by alayer layerofofPDMS, PDMS,thus thusrequiring requiringmore morepenetrative penetrativeelectrons. electrons. a layer of PDMS, thus requiring more penetrative electrons. The SEM images of MWCNTs dispersed in PDMS (Figure 3) were representative of the whole The TheSEM SEMimages imagesof ofMWCNTs MWCNTsdispersed dispersedin inPDMS PDMS(Figure (Figure3) 3)were wererepresentative representativeof ofthe thewhole whole surface. On the other hand, the SEM images of samples that were cut under liquid nitrogen in the surface. On the other hand, the SEM images of samples that were cut under liquid nitrogen in surface. On the other hand, the SEM images of samples that were cut under liquid nitrogen inthe the direction perpendicular to to the thesurface surfaceindicated indicated that there were MWCNTs the surface, direction that there were MWCNTs closeclose to thetosurface, which directionperpendicular perpendicular to the surface indicated that there were MWCNTs close to the surface, which were detected at a depth of no greater 5 μmthe from the edge. were detected at a depth no greater 5 than µm from edge. which were detected at aofdepth of no than greater than 5 μm from the edge.
Figure 3. SEM images: (a) PDMS/MWCNT (MWCNT: 1% w/w). (b) PDMS/MWCNT/CoFe2O4 Figure PDMS/MWCNT 1%1% w/w). (b)(b) PDMS/MWCNT/CoFe Figure3.3.SEM SEMimages: images:(a)(a) PDMS/MWCNT(MWCNT: (MWCNT: w/w). PDMS/MWCNT/CoFe 2O 2O 44 (MWCNT: 1% w/w; CoFe2O4: 2% w/w). The bright areas correspond to signals originating from the (MWCNT: The bright bright areas correspond to signals (MWCNT:1% 1%w/w; w/w; CoFe CoFe22O O44: 2% w/w). w/w). The signals originating originating from fromthe the heaviest elements associated to CoFe2O4 agglomerates. heaviest O44 agglomerates. agglomerates. heaviestelements elementsassociated associatedtotoCoFe CoFe22O
Additionally, as can be seen in Figure 3, for PDMS/MWCNT/CoFe2O4 composites, it was always Additionally, as as can be 3, for PDMS/MWCNT/CoFe 2O4 composites, it was always Additionally, beseen seenininFigure Figure 3, for PDMS/MWCNT/CoFe was 2 Oin 4 composites, observed that CoFe2Ocan 4 particles were grouped in clusters of 300–600 nm size, which itwere observed that CoFe 2O4 particles were grouped in clusters of 300–600 nm in size, which were always observed that CoFe O particles were grouped in clusters of 300–600 nm in size, which were 2 4 surrounded by MWCNTs (Figure 3). This result was confirmed by simultaneously recording AFM surrounded by byMWCNTs MWCNTs(Figure (Figure3). 3).This Thisresult resultwas wasconfirmed confirmedby bysimultaneously simultaneouslyrecording recordingAFM AFM surrounded and MFM images (Figure 4), and observing that magnetic signals recorded by MFM (provided by and MFM images (Figure 4), and observing that magnetic signals recorded by MFM (provided by andmagnetic MFM images (Figure and observing thatwith magnetic signals recorded by MFM (provided by the particles) were4),spatially coincident the AFM signals (provided by both MWCNTs themagnetic magneticparticles) particles)were werespatially spatiallycoincident coincidentwith withthe theAFM AFMsignals signals (provided (providedby byboth both MWCNTs MWCNTs the and magnetic particles), indicating that the nanotubes and magnetic particles were grouped, and magnetic particles), indicating that the nanotubes and magnetic particles were and magnetic particles),2O indicating that the nanotubes and magnetic particles were grouped, grouped, forming forming MWCNT/CoFe 4 clusters. That is, no “free” magnetic nanoparticles (not grouped to a forming MWCNT/CoFe 2O4 clusters. That is, no “free” magnetic nanoparticles (not grouped to a MWCNT/CoFe O clusters. That is, no “free” magnetic nanoparticles (not grouped to a MWCNT) 2 4 MWCNT) were detected, either by SEM or by AFM. MWCNT) were detected, either by AFM. SEM or by AFM. were detected, either by SEM or by
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Figure 4 2cured in (MWCNT: w/w; CoFe 4: CoFe 2% w/w). 4. PDMS/MWCNT/CoFe PDMS/MWCNT/CoFe O4 in cured inpresence the presence of H (MWCNT: 1% w/w; Figure 4. 4. PDMS/MWCNT/CoFe 2O24O cured thethe presence of of HH (MWCNT: 1%1% w/w; CoFe 2O24O : 2% w/w). 2 O4 : AFM image. MFM image. Exactly same region aregion given sample was scanned using 2% w/w). (a) AFM image. (b) MFM image. Exactly the same of a given sample was scanned (a)(a) AFM image. (b)(b) MFM image. Exactly thethe same region of of a given sample was scanned using thethe using the twoThe techniques. Thebetween coincidence between both images suggests that the magnetic and two techniques. The coincidence between both images suggests that the magnetic and non-magnetic two techniques. coincidence both images suggests that the magnetic and non-magnetic non-magnetic materials were grouped to form clusters, as also observed by SEM in Figure 3. materials were grouped to form clusters, as also observed by SEM in Figure 3. materials were grouped to form clusters, as also observed by SEM in Figure 3.
We made quantitative determinations the roughness, given the arithmetic average the We made quantitative determinations ofof the roughness, given byby the arithmetic average ofof the We made quantitative determinations of the roughness, given by the arithmetic average of the heights defined in Section 2.4 (Instrumentation) through the parameter R aOther . Other criteria, such heights defined in Section 2.4 (Instrumentation) through the parameter R a . criteria, such as heights defined in Section 2.4 (Instrumentation) through the parameter Ra . Other criteria, such as as geometric averagesor RMS values, areequivalent, equivalent, fact, arerendered rendered roughness geometric RMS values, inin fact, are totoroughness geometricaverages averages oror RMS values, areare equivalent, and,and, inand, fact, are rendered to roughness parameters parameters that are proportional a, in the sense when a increases, they increase also. parameters that are proportional toto RaR , in the sense that when RaRincreases, they increase also. that are proportional to Ra , in the sense that when Rthat a increases, they increase also. The dispersion of nanoparticles (PDMS + CoFe 24O 4,without without adding MWCNTs) didnot not The dispersion of nanoparticles (PDMS + CoFe 2 O , adding MWCNTs) The dispersion of nanoparticles (PDMS + CoFe2 O4 , without adding MWCNTs) did notdid introduce introduce significant changes in the roughness. In contrast, the roughness increased by a factor introduce significant changes in the roughness. contrast, the increased roughnessbyincreased a factor ofof+ significant changes in the roughness. In contrast,Inthe roughness a factor ofby3–5 in PDMS 3–5 PDMS MWCNT composites PDMS MWCNT CoFe 4 (the factoris isconsidered considered 3–5 ininPDMS + +MWCNT composites ininPDMS + +MWCNT + +CoFe 2O24O(the factor MWCNT composites and in PDMS and + and MWCNT + CoFe 2 O4 (the factor is considered with respect to with respect to PDMS in both cases). An additional increase in the roughness was observed the with respect to PDMS in both cases). An additional increase in the roughness was observed inin the PDMS in both cases). An additional increase in the roughness was observed in the systems cured in the systems cured in the presence of the magnetic field (H); the roughness in PDMS + MWCNT + systems cured inmagnetic the presence of the (H); the roughness in PDMS + MWCNT + presence of the field (H); themagnetic roughnessfield in PDMS + MWCNT + CoFe O + H was between 2 4 CoFe +H was between 2in and 3 times greater than in PDMS + MWCNT + CoFe 4. This increase CoFe 2O24O H was between 2 and 3 times than PDMS + MWCNT + CoFe 2O24O . This increase inin 2 and 3+4times greater than PDMS +greater MWCNT + in CoFe 2 O4 . This increase in the surface roughness a is clearly noted in the results presented in Figure 5. the surface roughness parameter R a isresults clearlypresented noted in the results5.presented in Figure 5. the surface roughness parameter parameter Ra is clearly noted inRthe in Figure
Figure 5.PDMS/filler PDMS/filler composites: Surface roughness. The altitude bars Figure 5. 5. composites: (a)(a) Surface roughness. The altitude of ofthe bars is is thethe average Figure PDMS/filler composites: (a) Surface roughness. The altitude ofthe the bars is the average roughness,RR consideringfour fourreplicates replicates each kind ofmaterial material andthree threeimages images each ,, considering four for each kind of of material andand three images for each sample. roughness, aR , aaconsidering forfor each kind forfor each a was calculated using 12 AFM images. The respective standard sample. That is, each reported That is,That each Ra wasRcalculated using 12using AFM The respective standardstandard deviation aRwas calculated 12images. AFM images. The respective sample. is,reported each reported deviation indicated on each bar. Height profiles recorded on straight lines indicated in is indicated on eachon bar. (b)bar. Height profiles recorded on theonstraight lines lines indicated in the deviation is is indicated each (b)(b) Height profiles recorded thethe straight indicated ininsets. thethe insets. PDMS, PDMS/MWCNT/CoFe 4and , PDMS/MWCNT/CoFe and(3)(3)PDMS/MWCNT/CoFe PDMS/MWCNT/CoFe 4incured (1) PDMS, (2) PDMS/MWCNT/CoFe the presence insets. (1)(1)PDMS, (2)(2)PDMS/MWCNT/CoFe 2O24O ,(3) 2O24Ocured in inthethe 2 O4 , and 2 O4 cured presence MWCNT: 1% w/w; 24O 4: 2% w/w. of H. MWCNT: 1% w/w; : 2% presence of of H.H. MWCNT: 1%CoFe w/w; CoFe 2Ow/w. : 2% w/w. 2O 4CoFe
Theabove aboveresults resultsdemonstrate demonstratethat thatcuring curingthe themagnetic magneticcomposite compositeunder underthe theaction actionofofa a The magnetic field induces a substantial increase in the surface roughness. The increase is expected magnetic field induces a substantial increase in the surface roughness. The increase is expected toto bebe dependentononthe theproportion proportionofofMWCNTs MWCNTsand andmagnetic magneticnanoparticles nanoparticlesdispersed dispersedininthe thepolymer, polymer, dependent
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The above results demonstrate that curing the magnetic composite under the action of a magnetic field induces a substantial increase in the surface roughness. The increase is expected to be dependent on the proportion of MWCNTs and magnetic nanoparticles dispersed in the polymer, and the intensity of the magnetic field. Although a systematic study of these variables is beyond the scope of the present work, the results are very conclusive concerning the effect of an enhanced roughness by applying magnetic fields in PDMS/MWCNT/CoFe2 O4 composites. 3.2. Films Exposed to Br2 (Liquid), Br2 (Gas) and UV In a first series of experiments, the films were impregnated with Br2 (liquid). Liquid drops of Br2 were deposited on the surface of the films by using Pasteur pipettes, under hood. The liquid mostly evaporated, although a part remained adsorbed (as the reddish colour, typical of bromine, was still observed on the films). After irradiating these samples with UV light for 1 h, it was observed with the naked eye that fractures and interruptions of the films were induced. The appearance of lines (scratches) in the films—randomly oriented, with dimensions in the order of 5 mm long and 1 mm wide, and corresponding to regions where the polymer film appeared destroyed—was detected, leaving the glass substrate exposed. That is, the mentioned treatment produced macroscopic damages, which could be observed by the naked eye. These damages were not detected in non-irradiated samples. Therefore, considering that liquid bromine impregnation produces (after UV irradiation) ruptures of the films at the macroscopic level, it was then decided that the samples would be exposed to bromine vapours. For this purpose, in a second series of experiments, the set-up and procedure described in Section 2.3 and Figure 1 were used in order to expose the films not to Br2 (liquid), but to Br2 (gas). After irradiation with UV light of the samples exposed to Br2 vapours, no damage, such as that observed when impregnating with liquid bromine, was observed under an optical microscope. However, the results of ATR, SEM and AFM showed significant changes in the samples at the microscopic level, as detailed below. In the following, we refer exclusively to samples that were exposed to bromine vapours and then irradiated. The presence of bromine was detected by energy-dispersive spectroscopy (EDS; coupled to the SEM instrument) in samples that were exposed to Br2 (g), but not irradiated. Moreover, in those samples exposed to Br2 (g) that were not washed with a saturated solution of Na2 S2 O3 before UV irradiation, the presence of micro-spherical drops of 200 nm diameters, which were attributed to adsorbed bromine agglomerates on the surface, was detected by SEM. These micro-droplets were not present in the samples that were washed with thiosulfate. The FTIR spectra of all irradiated (and washed) samples are shown in Figure 6. The spectra of the different samples presented similar characteristics, regardless of the substrate (aluminium or glass) and the method of preparation (spin-coating or tape methods). In some samples prepared on the glass substrate, the obtained spectrum was mounted on a very wide band of between 200 and 1000 cm−1 , which is assigned to glass; in some of the samples prepared on aluminium by spin-coating, it was observed that the bromine attacked the substrate (before UV irradiation). Figure 6b shows the irreversible disappearance, after UV irradiation, of the band at 910 cm−1 , which corresponds to the double bonds, –C=CH2 , of vinyl terminals of the siloxane chains [36]. It was also systematically observed that, after irradiation, there was a (partial) disappearance of the shoulder at 1060 cm−1 (Figure 6c), which is associated to Si–O–Si bonds [41]. No signals associated to MWCNTs (currently at 3400 and 1550 cm−1 [42]) were detected in PDMS/MWCNT composite films, likely due to a lack of instrumental sensitivity for the MWCNT concentrations used here. In summary, the FTIR spectra show that UV irradiation of the samples previously exposed to bromine vapours caused irreversible ruptures of the polymer chemical structure.
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Figure 6. FTIR-ATR spectra of PDMS films exposed to Br2 vapours before (…) and after (-) UV irradiation: (a–c) correspond to zooms of different spectral regions. Figure 6. FTIR-ATR spectra of PDMS films exposed to Br2 vapours before (…) and after (-) UV Figure 6. FTIR-ATR spectra of PDMS films exposed to Br2 vapours before ( . . . ) and after (-) UV irradiation: (a–c) correspond to zooms of different spectral regions. irradiation: correspond to of different spectral regions. 6.(a–c) FTIR-ATR of zooms PDMS films exposed to mechanism Br2 vapours before (…) and after (-) UV The Figure following is a spectra reasonable scheme of the of radical attack by Br• radicals irradiation: (a–c) correspond to zooms of different spectral regions. generated by UV radiation: The following is a reasonable scheme of the mechanism of radical attack by Br• radicals generated by UV radiation: The following is a reasonable scheme of the mechanism of radical attack by Br• radicals generated The following is a reasonable scheme of the mechanism of radical attack by Br• radicals Br2 + hν → 2 Br• (initiation) by UV radiation: generated by UV radiation:
Br2 + hν → 2 Br• (initiation)
H
Br2 + hν → 2 Br• (initiation)
H
→
+ Br•
+ Br•
+ HBr
→
+ Br•
H
→
•
•
+ HBr + HBr
•
Br Br
•
•
++ BrBr 22
+ Br2
2 Br•
→→
→
→ Br
Br
+ Br• + Br• + Br•
(termination)
2 Br• →→Br2Br 22Br• (termination) 2 (termination)
A large change in surface characteristics was observed in the samples exposed to bromine A large changeininsurface surface characteristics waswas observed in theinsamples exposed exposed to bromine A large change characteristics observed theThe samples to bromine vapours. Figures 7in and 8 present 2D and 3D was AFMobserved images, respectively. samples to that were not A large change surface characteristics in the samples exposed bromine vapours. vapours. Figures 7 and 8 present 2D and 3D AFM images, respectively. The samples that were not vapours. 7 and 8 present 2D and 3Dcompared AFM images, respectively. exposedFigures to bromine vapours appeared “flat”, to those that were. The samples that were not exposed to 8bromine vapours appeared “flat”, compared to those that were. Figures 7 and present 2D and 3D AFM images, respectively. The samples that were not exposed to exposedIt to vapours appeared “flat”, compared to those that were. isisbromine clear exposure to vapours theabsence absence UV irradiation with lamp, clearthat that exposure to bromine bromine vapours ininthe ofof UV irradiation with the the lamp, bromine It vapours appeared “flat”, compared to those that were. It is clear that exposure to bromine vapours in the absence of UV irradiation with the lamp, likely due to spurious UV from the ambient source, induced the appearance of surface wells, likely due that to spurious UVtofrom the ambient source, the of surface wells, It is clear exposure bromine vapours indepths: theinduced absence of appearance UV irradiation with the lamp, likely 2 and presenting given ofthe wellambient areasand andsource, areas from 0 to 30 depths from wells, 2 and likely due tothe spurious UV fromof induced of from surface presenting the givendistribution distribution well areas depths: areas from 0the to 30appearance μmμm depths due15totospurious UV from the ambient source, induced the appearance of surface wells, presenting the 2 and nm 9a–c). withthe theUV UV lamp,the the distribution of areas and from 15 to225 225the nm(Figure (Figuredistribution 9a–c). After After irradiation irradiation with lamp, distribution and presenting given of well areas and depths: areas from 0 of tosurface 30surface μmareas depths 2 and depths from 15 to 225 nm 2 given distribution of well areas and depths: areas from 0 to 30 µm 2 and depths became broader, and wells with surface surfacewith areasthe from μm a depth distribution from depths became broader, and wellsirradiation with areas from 0 0toto 9595 μm a depth distribution from 15 to 225 nm (Figure 9a–c). After UV lamp, theand distribution of surface areas and (Figure 9a–c). After with 9b–d). the UV lamp, the distribution of surface areas and depths became 7575 toto 500 were observed 9b–d). 500nm nm wereirradiation observed (Figure (Figure 2
depths became broader, and wells with surface areas from 0 to 95 μm and a depth distribution from broader, and wells with surface areas from 0 to 95 µm2 and a depth distribution from 75 to 500 nm 75 to 500 nm were observed (Figure 9b–d). were observed (Figure 9b–d).
Figure 7. Examples of 3D AFM images: (a) Pristine PDMS. (b) UV-irradiated sample. (c) Sample
Figure 7. Examples of 3D AFM images: (a) Pristine PDMS. (b) UV-irradiated sample. (c) Sample exposed to Br2 (g), but not irradiated. (d) Sample exposed to Br2 (g) and then UV-irradiated. exposed to Br2 (g), but not irradiated. (d) Sample exposed to Br2 (g) and then UV-irradiated.
Figure Examples of of 3D Figure 7. 7. Examples 3D AFM AFM images: images: (a) (a) Pristine Pristine PDMS. PDMS. (b) (b) UV-irradiated UV-irradiated sample. sample. (c) (c) Sample Sample exposed to Br (g), but not irradiated. (d) Sample exposed to Br (g) and then UV-irradiated. 2 2 exposed to Br2 (g), but not irradiated. (d) Sample exposed to Br2 (g) and then UV-irradiated.
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Figure8. 8.Examples Examples of 2D AFM profiles: (a) Sample of pristine PDMS. (b) UV-irradiated sample. Figure of 2D AFM profiles: (a) Sample of pristine PDMS. (b) UV-irradiated sample. (c) Figure 8. Examples of 2D AFM profiles: (a) Sample of pristine PDMS. (b) UV-irradiated sample. (c) (c) Sample exposed to but Br2not (g), but not(d) irradiated. (d) Sample irradiated. Sample exposed to Br2 (g)exposed followedtobyBr UV-irradiation. Sample exposed to Br2 (g), 2 (g) followed Sample exposed to Br2 (g), but not irradiated. (d) Sample exposed to Br2 (g) followed by UV-irradiation. by UV-irradiation.
Figure 9. Well surface area histograms for bromine-treated samples: (a) PDMS + Br2 composite, and Figure surfacearea areahistograms histogramsfor forbromine-treated bromine-treated samples: PDMS + 2Brcomposite, 2 composite, Figure 9. 9. Well Well surface samples: (a)(a) PDMS + Br andand (b) (c) PDMS + (b) PDMS + Br2 + UV composite. The well depth histogram for bromide-treated sample: 2 + UV composite. The well depth histogram for bromide-treated sample: (c) PDMS (b) PDMS + Br PDMS + Br2 + UV composite. The well depth histogram for bromide-treated sample: (c) PDMS + Br+2 Br2 composite, and (d) PDMS + Br2 + UV. Here, n is the number of wells detected in the 12 AFM Br 2 composite, (d) PDMS 2 + Here, UV. Here, n isnumber the number of detected wells detected in AFM the 12images AFM composite, andand (d) PDMS + Br2+ +BrUV. n is the of wells in the 12 images used to produce the histograms. images to produce the histograms. used to used produce the histograms.
Figure Figure1010shows showsthe theheight heightprofiles profiles(in (innm) nm)calculated calculatedon ona astraight straightline lineofof5050μm μmlength lengthfor foreach each Figure 10 shows the height profiles (in nm) calculated on straight line of+50 µm length for each sample. Clearly, the height profiles follow the same trend as R a: aPDMS ≈ PDMS UV < PDMS + Br 2< sample. Clearly, the height profiles follow the same trend as Ra: PDMS ≈ PDMS + UV < PDMS + Br 2< sample. Clearly, the height profiles follow the same trend as R : PDMS ≈ PDMS + UV < PDMS + Br a 2< 2 + UV. PDMS 2 + UV. PDMS+ +BrBr PDMS + Br2 + UV. observed by AFM increased in the expected sequence: PDMS ≈ PDMS + UV < The Theroughness roughness observed by AFM increased in the expected sequence: PDMS ≈ PDMS + UV < The roughness AFM increased in the expected sequence: PDMS ≈ PDMS + UV PDMS + Br 2 < PDMS +observed Br2 + UV.by The mean roughness Ra and standard deviation (average values on < PDMS + Br 2 < PDMS + Br2 + UV. The mean roughness Ra and standard deviation (average values on PDMS + Br < PDMS + Br + UV. The mean roughness R and standard deviation (average values on a 2 2 four fourreplicates replicatesfor foreach eachcomposition) composition)are areshown shownininFigure Figure11A. 11A.The Themean meandepths depthsfor forwells wellspresented presented four replicates forwith each composition) are shown in Figure 11A. The mean depths for wells presented in inin samples samplestreated treated withbromide bromideare areshown shownininFigure Figure11B. 11B. samples treated with bromide are shown in Figure 11B.
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Height (nm) Height (nm)
11 of 15 11 of 15 11 of 15
PDMS PDMS
PDMS + UV PDMS + UV
PDMS + Br2 PDMS + Br2
PDMS+Br2+UV PDMS+Br2+UV
X (µm) X (µm) Figure 10. Height profiles of AFM, calculated on the images and lines shown below. The symbol X Figure 10. Height profiles of AFM, calculated on the images and lines shown below. The symbol X Figure 10. Height profiles of calculated on theline, images and lines below. symbol X (μm) onAFM, the indicated indicated straight measured fromshown the left left to the theThe right. (µm) represents represents aa distance distance on the straight line, measured from the to right. (μm) represents a distance on the indicated straight line, measured from the left to the right.
Figure 11. (A) Average surface roughness, Ra. (B) Mean well depth for the bromide-treated samples. Figure 11.surface (A)Average Average surface roughness, Ra .(B) (B) Meanreplicated welldepth depth forthe thebromide-treated bromide-treated samples. Figure 11. (A) surface Ra. well for samples. (C) Mean area of wells.roughness, The dispersions ofMean four samples (considering three images (C) Mean surface area of wells. The dispersions of four replicated samples (considering three images (C) surface area of wells. The dispersions of four replicated samples (considering three images perMean sample) are indicated by segments on each bar. per sample) are indicated by segments on each bar. per sample) are indicated by segments on each bar.
4. Conclusions Conclusions 4.4.Conclusions The two methods explored in this work led to an increase in the surface roughness, which was Thetwo two methods explored inInthis work to an of increase inphysical the surface roughness, The explored work ledled to an increase in the surface roughness, whichwhich was quantified bymethods the parameter Rin a. this the first, the use a more method, which used was quantified by the parameter R . In the first, the use of a more physical method, which used a quantified by the parameter a. increase In the first, use of awhen more method, used MWCNT/CoFe 2O4 fillers, gave R an in thethe roughness thephysical PDMS films werewhich cured in the MWCNT/CoFe gave increase in the roughness when PDMS cured in 24Ofillers, 4 fillers, MWCNT/CoFe 2O gave an an increase in the roughness the the PDMS filmsfilms werewere cured in the presence of a magnetic field, H, which was remarkable in when comparison to those cured without the the presence of a magnetic field, H, which was remarkable comparison tothose thosecured cured without the presence of magnetic field, H, systems which was remarkable in in comparison the presence of aH. For example, in that were not cured with H, Rto a increased by awithout factor of 5 presence of H. For example, in systems that were not cured with H, R increased by a factor of 5 when a Ra increased presence Forand example, in systems thatdispersed, were not while cured the withincrease H, by awhen factorthese of 5 when nanotubes nanoparticles were was 11-fold nanotubes andcured nanoparticles were dispersed, while the while increase was 11-foldwas when these systems were when nanotubes and dispersed, increase 11-fold when these systems were in nanoparticles the presence ofwere H perpendicular to thethe surface. cured in the presence of H perpendicular to the surface. systems were cured in the presence of H perpendicular to the surface. On the other hand, the chemical method of exposure to bromine vapours followed by UV On the theproduced other hand, hand, the chemical chemical methodwells of exposure exposure to bromine bromine vapours followed by nm. UV On other the method of to vapours followed by UV irradiation drastic surface changes; had depths in the range from 75 to 500 irradiationthe produced drastic surface changes; wells had depths the(with range from 75totoinfluence 500nm. nm. irradiation produced drastic surface wells depths ininthe range from 75 500 Although wells were generated bychanges; the exposure tohad bromine vapours the possible Although the wells were generated by the exposure to bromine vapours (with the possible influence Although theUV wells were generated by the exposure (with the possible influence of spurious radiation from the ambient source), to thebromine area of vapours these wells increased by a factor of 3 ofspurious spurious UVradiation radiation from theambient ambientsource), source),the thearea areaof ofthese thesewells wellsincreased increasedby byaafactor factorof of33 of UV the when irradiating with thefrom UV lamp. whenAlthough irradiating with the UV UV lamp. when irradiating with the lamp. the primary aim was not to compare the methods, the question addressed to the Although the primary aim was not not to to compare compare the methods, thegenerate question addressed to the the Although the naturally. primary aim methods, the question addressed comparison arises For was instance, the physicalthe method did not large surfaceto wells, comparison arisesnaturally. naturally. Forinstance, instance, thephysical physical method didnot not generateof large surface wells, comparison For method did generate large surface wells, which were arises induced on the surface by the the chemical attack, but many properties the films changed which were induced on the surface by the chemical attack, but many properties of the films changed which were induced on the surface by the chemical attack, but many properties of the films changed when filler particles were added. For example, the nanocomposites displayed superparamagnetism whenfiller filler particles particles were added. For Forwere example, the nanocomposites nanocomposites displayed superparamagnetism when were added. example, the displayed superparamagnetism when small magnetic nanoparticles included, and in some cases, the films may have become when small magnetic nanoparticles wereamounts included,ofand in some were cases,dispersed. the films may have become electrical conductors if relatively large MWCNTs These changes in electrical if relatively amountsprocesses of MWCNTs dispersed. changes for in physical conductors properties induced by large the physical may were or may not be These of relevance physical properties induced by the physical processes may or may not be of relevance for
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when small magnetic nanoparticles were included, and in some cases, the films may have become electrical conductors if relatively large amounts of MWCNTs were dispersed. These changes in physical properties induced by the physical processes may or may not be of relevance for applications. For instance, in the case of applications as antifouling agents, the mentioned changes are not of central importance; the relevant variable is the change of surface topology, given by the increase of roughness, the creation of wells, etc. On the other hand, in the case of applications for microfluidics, the generation of magnetic surfaces can be of central importance for designing micro-valves or actuators. In the physical method, the roughness could be modified mainly by changing the amount of MWCNTs. We verified that the roughness increased when increasing the proportion MWCNT/PDMS. From a practical point of view, the amount of MWCNTs is limited by costs and by the fact that the above concentration threshold in the presence of MWCNTs can drastically perturb many physical properties of the composite, such as electric and thermal conductivities. In the chemical method, the exposure to UV radiation was the main factor to control (the concentration of Br2 adsorbed on the surface is hard to change, as it is determined by the bromine vapour pressure at room temperature). If the incident power is fixed, then the roughness is increased by increasing the exposition time, up to a plateau. For instance, we have observed that, under the present instrumental conditions, no further roughness increase was noted for exposition times above 15 minutes. Below this time, it is possible, with the experimental set-up used in this work, to have a (partial) control of the roughness by changing the exposition time, although a series of systematic studies are required to quantify the effects on the roughness. A comparison of the effect on the roughness between both methods is possible; however, it requires some care, as it is clear that the chemical method does generate wells, while the physical method does not. Nevertheless, we can say that the largest roughness increase was obtained for (PDMS + R − Ra (PDMS) Br2 (gas) + UV). Moreover, defining the relative roughness R as R ≡ aR (PDMS × 100, then the ) a following sequence is obtained: R(PDMS) ≈ R(PDMS + UV) ≈ 0 < R(PDMS + MWCNT + CoFe2 O4 ) ≈ R(PDMS + Br2 (g)) ≈ 400 < R(PDMS + MWCNT + CoFe2 O4 + H) ≈ 1000 < R(PDMS + Br2 (g) + UV) ≈ 3000. Although these values are dependent on the concentration of nanomaterials, the intensity of the magnetic field, and the UV conditions, they clearly indicate that both—(nanomaterials + H) and (Br2 + UV)—induce large surface changes. The increase of Ra reported in the present work, for systems that were not cured in the presence of magnetic field, is similar to those reported by other authors [10,11,26], although our values and the values reported by these authors were both dependent on the specific conditions. However, it is noteworthy that curing in the presence of magnetic fields induces Ra values greater than those previously reported. On the other hand, the chemical attack method induced by bromine radicals generated by UV radiation produces not only an increase in Ra , but also the occurrence of wells, whose depths are quantified by the mean height parameter. Although, to the extent of our knowledge, we have not detected reports of a quantification of these effects in the literature, the Ra parameter reported here for the chemical attack process was even greater than that measured for the physical process. The surface effects were, in this case, similar to or higher than those reported in references [12,18,19]. Both processes reported here are suitable for different applications. For instance, the physical process using the nanocomposite approach is interesting for cases in which the nanomaterial is not only responsible for the surface roughness increasing, but also poses a well-defined physical property, such as electrical conduction, thermal conduction, magnetism or magneto resistance. Considering the case of developing micro-valves for biochemical applications in which the surface of the materials is modified by using magnetic fillers, the roughness increase may avoid/reduce the formation of bacterial films, while the magnetic character can be used to open/close a valve. In the case of developing sensors, the roughness increase can provide adsorption sites for an analyte, while electrical signals are driven through the composite if conducting nanofillers are included. Thus, although the physical approach is relatively expensive, as it requires loading the polymer with nanomaterials, it finds applications in sensors and actuators for which a modified surface is required in combination with a response given
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by a physical property (magnetism, conductivity, etc.). On the other hand, the chemical attack does not require nanomaterials; thus, the costs are, in principle, lower, in comparison to the nanocomposite approach. The chemical process does not introduce a new physical property to the polymer (such as magnetism), it simply creates strong perturbations to the topology of the films. Thus, the chemical attack seems to be more suitable for situations in which it is needed only to protect a surface for biofilm formation. To the extent of our knowledge, the present study constitutes the first report of increasing surface roughnesses using the described methods. Each method induces a different characteristic on the surface, and the eventual selection of which is used will depend on the particular application desired. Acknowledgments: Leonardo Lizarraga, Norma Beatriz D´Accorso and Ricardo Martín Negri are research members of the National Council of Research and Technology (CONICET, Argentina). Financial support was received from UBA (UBACyT project 20020150100079BA) and the Ministry of Science, Technology and Innovations (MINCYT-FONCYT, Argentina, PICT 2011-0377). The Center of Advanced Microscopy (CAM), UBA, is acknowledged for the SEM images. Author Contributions: Jorge Nicolas Cabrera prepared the samples and performed most of the experimental determinations. Mariano Ruiz made the initial determinations of the composites. Mirta Fascio and Norma D’Accorso designed the experiments with bromide, provided materials and instrumentation, and participated in the discussion of the manuscript. Rosica Mincheva and Philippe Dubois conceived and designed some of the experiments, as well as were involved in the writing of the manuscript. Leonardo Lizarraga was responsible for the AFM determinations and data analysis. R. Martin Negri conceived the experiments and wrote most parts of the manuscript. Conflicts of Interest: The authors declare no conflict of interest.
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