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In this paper, the number associated with the solvent, e.g., hexanes (8) indicates the rank of the solvent from Figure 1, in descending order of solvability in PDMS.
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h for each solvent, but these data are not available for many solvents.
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1H NMR spectrum of a solution that was allowed to flow through these channels for 24 h showed the absense of diisopropylamine.
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By placing nonextracted pieces of PDMS in a 90 °C oven for ∼10 min after contact, we obtained irreversible sealing as long as 1 h after plasma treatment. We found that this procedure was not always reproducible, however.
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39
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0345186093
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note
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To prepare the oxidized surfaces, pieces of PDMS were oxidized in a plasma, allowed to stand in contact with ambient air for 1 min at room temperature, contacted, and immediately placed in a 90 °C oven for 10-20 min.
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0344755825
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note
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Pieces of PDMS began losing their shape and became gellike after being immersed in dipropylamine for 36 days.
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50
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0345618233
-
-
note
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From the low-solubility solvents listed in Figure 1, pyridine, NMP, DMF, and DMSO cross-linked the PDMS prepolymer into a clumpy gel upon mixing.
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51
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0344323628
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note
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There are some solutes, however, that are more likely than others to partition into PDMS. For example, solutes that have a chemical structure similar to the extremely soluble solvents (e.g., diisopropylamine and triethylamine) will likely partition into the polymer more than solutes that have characteristics of the low-solubility solvents (such as alcohols and ketones). The high solubility of amines in PDMS may explain why the partition ratio of rhodamine was quite low in the PDMS-water mixture (i.e., rhodamine favored the PDMS phase over the water phase, Table 5).
-
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Both α and χ are temperature-dependent, dimensionless parameters that represent the enthalpy term in the Gibbs free energy equation. The difference between the parameters is that α represents the pair-pair interaction energy in a solvent-solute solution (i.e., the solvent molecule-solute molecule interaction), while χ represents two types of interactions in a polymer-solvent solution: pair-pair interaction energy (i.e., the segment-segment interaction of the polymer) and the polymer volume and solvent volume interaction. Since χ involves volume interactions, it contains an entropic contribution, making it not as straightforward to interpret as the α term. For general discussion in this paper, however, we compare the values of α and χ directly. (For further discussion, refer to the section on Flory-Huggins Theory in: Young, R. J. Introduction to Polymers; Chapman and Hall: New York, 1991.)
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0345186092
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The amount of un-cross-linked PDMS in the bulk polymer depends on the ratio of PDMS prepolymer to cross-linking agent (a 10:1 (w/w) ratio is recommended), as well as the degree of mixing of the two components. A well-mixed solution of PDMS will contain less un-cross-linked PDMS than a solution that is not well-mixed. The amount of extracted PDMS depends on the efficiency of the solvent to swell the polymer.
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Since the reagents flow at a rate of ∼44 mL/min and are adequately mixed in the channel, it should take ∼40 s for the reagents to reach the outlet for a channel with dimensions 200 μm × 75 μm × 20 cm (whl). The time for reaction is ≪ 40 s (Gilani, S. S. H.; Triggle, D. J. J. Org. Chem. 1966, 31, 2397-2398). Thus, the reaction should take place in the channel and not at the outlet. Observations of color change within the channel, and not at the outlet, agree with this analysis.
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We may not have observed swelling of PDMS with benzene in this experiment because of the short length of time in which the solvent was in contact with the polymer (15 min for the experiment performed here, versus 24 h for the swelling experiment performed in Figure 1, where swelling was observed).
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Typically, equilibrium swelling was reached within 1 h of being immersed in the solvent. For the amines, however, equilibrium swelling time varied from days to weeks.
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71
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0345618231
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note
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We assumed the PDMS to have an average molecular weight of 50 000 based on the viscosity of the polymer immediately after mixing with the curing agent (4000 mPa/s) (www.dowcorning.com) and the relationships between viscosity and molecular weight for PDMS (https://www.sigma-aldrich.com/ aldrich/brochure/al_pp_viscosity.pdf).
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