This work has been supported by Western Kentucky University&#8217;s Ogden College of Science and Engineering, including internal support from the Department of Chemistry and from the Office of Research (RCAP 13-8032). The assistance of Dr. John Andersland at the WKU Microscopy Facility (SEM images) and Associate Professor Yan Cao of the WKU Institute for Combustion Science and Engineering (BET analysis) has been central to conducting this work.

1. Preparation of Emulsion
<ol>
	<li>Emulsion Contents
	<ol>
		<li>Mass an appropriate amount of salt to produce 10 ml of 0.03-M solution. For platinum(IV) chloride measure 0.101 g, for zinc(II) chloride (ZnCl2) measure 0.032 g, and sodium chloride (NaCl) measure 0.018 g.</li>
		<li>In individual test tubes, dissolve each salt into 10 ml of DI water. Set aside for later use.</li>
		<li>Use a 20-ml, sealable glass vial for the contents throughout this procedure. Tare a balance to the glass vial.</li>
		<li>We...

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The authors have nothing to disclose.

The beads produced using this protocol (and by adjusting the electrolyte concentration and identity) are fundamentally different from those produced with a low-ionic strength emulsion, as seen by comparison of Figure 1A to the other SEM images in Figure 1. Our initial report used PtCl4 with the intention of further catalyzing the polymerization cross-linking at the aqueous-aliphatic interface14. In that report, large concave indentations were seen. Since that report...

Polydimethylsiloxane (PDMS) is one of the most widely used silicone compounds. Its biocompatibility has led to widespread use in implant and other biomedical engineering structures1,2. It is trivially cross-linked into elastic structures using an organosilyl compound (such as triethoxysilane), a simple and reliable procedure which has made it useful for cast polymer applications where some flexibility is required3. Once cross-linked, PDMS is largely inert, particularly in biological conditions, and is therefore useful for a variety of food and medical applications4,5. Ease of casting, chemical inertness, and hydrophobicity have made it a natural choice for microfluidic devices6,7. Its affinity for non-halogenated, non-polar organic compounds has made it a popular stationary phase in separations chemistry8-10. 
Recently, microbubble fabrications have been used to generate porous beads for use as catalyst structural substrates or in chemical separations11,12. In both applications, ideal materials will have a maximized surface-area-to-volume (SAV) ratio for best efficiency. In a microbubble fabrication process, microstructuring of materials is typically accomplished by isolating the polymer in aliphatic &#8220;microbubbles&#8221; by emulsification in an aqueous continuous phase. The initial report of microporous PDMS beads produced them by mechanical emulsification of two phases (aliphatic and aqueous)13. The stock PDMS liquid (and its cross-linking agent) is dissolved into the aliphatic phase, which is structured into microscopic beads by being forced to cavitate within the (continuous) aqueous phase. The emulsification is stabilized by the addition of a non-ionic surfactant. When the emulsion is added dropwise to a heated bath, solid beads form by agglomeration of the microbubbles into clusters of tiny spheres of cross-linked PDMS. Our goal in this protocol is to modify this procedure to develop beads with an inverted porosity to improve the SAV ratio of the material.
As reported previously, control of the beads can be directed to some extent by the aliphatic:aqueous ratios in the emulsion. However, we have reported recently that addition of platinum(IV) chloride (PtCl4) inverts the porosity: materials are formed in which the PDMS is riddled with concave pores14. This indicates that the aqueous layer cavitates inside the aliphatic one, despite having similar aliphatic:aqueous ratios to those published in the original work13. The primary advantage of our method is that this concave porosity should naturally result in an increased SAV ratio, and thus, improved efficiency for analytical chemistry applications. While we are continuing to explore the specific effects of the addition of the platinum compound, we show here that the same effect can be accomplished using any aqueously soluble ionic compound, though perhaps to a reduced extent. Because our techniques also differ in some key aspects from what has been previously reported, we present our protocols here as a video to encourage others to extend our methods. Most notably, we use a common bath sonicator of the type used to clean glassware or other equipment, rather than the (considerably more expensive) probe sonicator often used in microbubble fabrication. This adjusted approach to the microbubble fabrication procedure could potentially be extended for the production of large quantities of bulk materials as well, creating porous sheets or slabs which could have applications for biomedical devices, aerospace and automotive industry, or substrates for chemical catalysis. Users seeking to generate high-SAV-ratio, microstructured materials using other similar polymers for such analyses may find that our protocols can be extended to any polymer for which the microbubble emulsion technique can be applied.

<table border="0">
	<tbody>
		<tr>
			<td>Poly(dimethylsiloxane), vinyl terminated</td>
			<td>Sigma-Aldrich</td>
			<td>68083-19-2</td>
			<td></td>
		</tr>
		<tr>
			<td>n-Heptane</td>
			<td>Sigma-Aldrich</td>
			<td>142-82-5</td>
			<td>Flammable</td>
		</tr>
		<tr>
			<td>Triethoxysilane</td>
			<td>Sigma-Aldrich</td>
			<td>998-30-1</td>
			<td>Flammable, Accutely Toxic</td>
		</tr>
		<tr>
			<td>Sorbitan Monoleate (Span-80)</td>
			<td>Fluker</td>
			<td>1338-43-8</td>
			<td></td>
		</tr>
		<tr>
			<td>Platinum (IV) Chloride</td>
			<td>Sigma-Aldrich</td>
			<td>13454-96-1</td>
			<td>Accutely Toxic</td>
		</tr>
		<tr>
			<td>Zinc (II) Chloride</td>
			<td>Sigma-Aldrich</td>
			<td>7646-85-7</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium Chloride</td>
			<td>Sigma-Aldrich</td>
			<td>7647-14-5</td>
			<td></td>
		</tr>
		<tr>
			<td>2.8L Water Bath Sonicator</td>
			<td>VWR</td>
			<td>97043-964</td>
			<td></td>
		</tr>
	</tbody>
</table>

microbubble fabrication of concave-porosity pdms beads

Microbubble fabrication (by use of a fine emulsion) provides a means of increasing the surface-area-to-volume (SAV) ratio of polymer materials, which is particularly useful for separations applications. Porous polydimethylsiloxane (PDMS) beads can be produced by heat-curing such an emulsion, allowing the interface between the aqueous and aliphatic phases to mold the morphology of the polymer. In the procedures described here, both polymer and crosslinker (triethoxysilane) are sonicated together in a cold-bath sonicator. Following a period of cross-linking, emulsions are added dropwise to a hot surfactant solution, allowing the aqueous phase of the emulsion to separate, and forming porous polymer beads. We demonstrate that this method can be tuned, and the SAV ratio optimized, by adjusting the electrolyte content of the aqueous phase in the emulsion. Beads produced in this way are imaged with scanning electron microscopy, and representative SAV ratios are determined using Brunauer&#8211;Emmett&#8211;Teller (BET) analysis. Considerable variability with the electrolyte identity is observed, but the general trend is consistent: there is a maximum in SAV obtained at a specific concentration, after which porosity decreases markedly.

Representative SEM images of beads arising from emulsions with different electrolyte conditions are shown in Figure 1. Figure 1A shows a bead similar to those obtained by DuFaud, et al.13, produced using our procedures, without the addition of any electrolyte. Beads shown in Figure 1B-D, resulting in different morphologies for each metal ion. For all images shown, 300 &#956;l of 0.03-M electrolyte solutions were used in place of 300 &#956;l of the DI ...

Watch this Scientific Journal Video about Microbubble Fabrication of Concave-porosity PDMS Beads at JoVE.com

Microbubble Fabrication of Concave-porosity PDMS Beads

Procedures used to generate microstructured concave-porosity polydimethylsiloxane beads are presented. Effects of electrolyte concentration and identity within the aqueous phase are particularly emphasized.

Microbubble fabrication (by use of a fine emulsion) provides a means of increasing the surface-area-to-volume (SAV) ratio of polymer materials, which is ...

microbubble-fabrication-of-concave-porosity-pdms-beads

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JoVE Journal

Chemistry

8.2K Görüntüleme.  Western Kentucky University. Procedures used to generate microstructured concave-porosity polydimethylsiloxane beads are presented. Effects of electrolyte concentration and identity within the aqueous phase are particularly emphasized. 