Contact angle goniometry

Contact angle goniometry was performed on functionalised glass cover slips with three probe liquids. Glass cover slips were selected as sample substrates since flat surfaces enable more accurate contact angle measurement than curved surfaces (such as glass vials). Measurement of contact angle allows the calculation of surface energy of the templates which is a significant factor in determining template interaction with solution. Low surface energy is commonly associated with hydrophobic material with low wettability. Conversely, liquid spreads easily on surfaces with high surface energy.

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Owens and Wendt altered this approach by grouping non-bonding London, Debye and Keesom interaction into single dispersive component and the rest of the terms into one polar component (Owens & Wendt, 1969). Using Berthelot’s principle, Owen’s-Wendt method provides the following relationship:

𝛾𝛾𝑆𝑆𝐿𝐿 = 𝛾𝛾𝑆𝑆𝐿𝐿+ 𝛾𝛾𝐿𝐿𝐿𝐿− 2�𝛾𝛾𝑆𝑆𝐿𝐿𝑑𝑑𝛾𝛾𝐿𝐿𝐿𝐿𝑑𝑑 − 2�𝛾𝛾𝑆𝑆𝐿𝐿𝑝𝑝𝛾𝛾𝐿𝐿𝐿𝐿𝑝𝑝 ( 4.3 )

By combining Young’s equation with equation 4.3, solid surface energy and contact angle are related by the equation,

(1+𝑐𝑐𝑠𝑠𝑠𝑠𝑐𝑐)𝛾𝛾𝑆𝑆𝐿𝐿 2�𝛾𝛾_{𝑆𝑆𝐿𝐿}𝑑𝑑 = �𝛾𝛾𝑆𝑆𝐿𝐿 𝑝𝑝 _{× �}𝛾𝛾𝑆𝑆𝐿𝐿𝑝𝑝 𝛾𝛾_{𝑆𝑆𝐿𝐿}𝑑𝑑 + �𝛾𝛾𝑆𝑆𝐿𝐿𝑑𝑑 ( 4.4 ) When (1+𝑐𝑐𝑠𝑠𝑠𝑠𝑐𝑐)𝛾𝛾𝑆𝑆𝐿𝐿 2�𝛾𝛾_{𝑆𝑆𝐿𝐿}𝑑𝑑 is plotted against � 𝛾𝛾_{𝑆𝑆𝐿𝐿}𝑝𝑝

𝛾𝛾_{𝑆𝑆𝐿𝐿}𝑑𝑑 , square of the intercept provides the solid dispersive energy and square of the slope provides polar surface energy of the solid phase.

Another approach in determining components of surface energy was proposed by van Oss, Chaudhury and Good by dividing surface energy in long range interactions involving Lifshitz-van der Waals component ( 𝛾𝛾𝐿𝐿𝐿𝐿 ₎ (consisting of London, Keesom and Debye interactions) and short range interactions termed acid-base component (𝛾𝛾𝐴𝐴𝐵𝐵_{) (Carel J. Van Oss et al., 1988;} Van Oss et al., 1986). Acid-base component is further divided into acidic (𝛾𝛾+₎ and basic (𝛾𝛾−_{) constituents and related by the equation,}

𝛾𝛾𝐴𝐴𝐵𝐵 _{= 2�𝛾𝛾}+_𝛾𝛾− _{( 4.5 )}

The interfacial interactions can then be written as,

𝛾𝛾𝑆𝑆𝐿𝐿 = 𝛾𝛾𝑆𝑆𝐿𝐿+ 𝛾𝛾𝐿𝐿𝐿𝐿 − 2�𝛾𝛾𝑆𝑆𝐿𝐿𝐿𝐿𝐿𝐿𝛾𝛾𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿− 2�𝛾𝛾𝑆𝑆𝐿𝐿+𝛾𝛾𝐿𝐿𝐿𝐿− − 2�𝛾𝛾𝑆𝑆𝐿𝐿−𝛾𝛾𝐿𝐿𝐿𝐿+ ( 4.6 )

By combining equation 4.6 with Young’s equation, the surface energy and contact angle relationship as per acid-base approach can be written as,

𝛾𝛾𝐿𝐿𝐿𝐿(1 + 𝑐𝑐𝑐𝑐𝑐𝑐𝜃𝜃) = 2�𝛾𝛾𝑆𝑆𝐿𝐿𝐿𝐿𝐿𝐿𝛾𝛾𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿+ 2�𝛾𝛾𝑆𝑆𝐿𝐿+𝛾𝛾𝐿𝐿𝐿𝐿− + 2�𝛾𝛾𝑆𝑆𝐿𝐿−𝛾𝛾𝐿𝐿𝐿𝐿+ ( 4.7 )

If contact angle of three probe liquids with at least two having polar components are known, surface energy of a solid surface can be calculated using both Owens-Wendt (OW) and acid-base (vOCG) approaches. The surface tensions of probe liquids required for these calculations are provided in Table 4.3. Advancing contact angle of the probe liquids on template surfaces are provided in Table 4.4.

Solvent

vOCG approach OW approach

𝜸𝜸𝑳𝑳𝑳𝑳𝑳𝑳𝑳𝑳 𝜸𝜸𝑳𝑳𝑳𝑳+ 𝜸𝜸𝑳𝑳𝑳𝑳− 𝜸𝜸𝑳𝑳𝑳𝑳 𝜸𝜸𝑳𝑳𝑳𝑳𝒅𝒅 𝜸𝜸𝑳𝑳𝑳𝑳𝒑𝒑 𝜸𝜸𝑳𝑳𝑳𝑳

Water 26.2 48.5 11.1 72.8 21.8 51.0 72.8

Diiodomethane 50.8 0.0 0.0 50.8 50.8 0.0 50.8

Formamide 35.5 11.3 11.3 58.0 39.0 19.0 58.0

Table 4.3. Surface energy values of probe liquids in mJ/m2_{.[vOCG approach} solvent energy values (Della Volpe et al., 2004), OW approach solvent energy values (Volpe & Siboni, 1997)]

Cyano Mercapto Fluoro Water 55.2 ± 1.7 74.9 ± 2.7 96.4 ± 3.2

Diiodomethane 35.3 ± 3.4 36.4 ± 2.2 74.3 ± 2.4

Formamide 38.8 ± 2.1 58.1 ± 1.3 83.0 ± 1.8 Table 4.4. Advancing contact angle (°) of probe liquids on template surfaces.

Advancing contact angles of probe liquids on templates were utilised to calculate surface energy of templates using both OW and vOCG approaches. Surface energy values computed through both methods are provided in Table 4.5. Surface energy values reveal that, among the three template chemistries, cyano functional group results in surfaces with the highest energy while fluoro functional groups results in least surface energy. Dispersive surface energy component of cyano and mercapto functionalised templates calculated through OW method are similar with a negligible difference of 0.4 mJ/m2_{. Similar} result is also observed in the Lifshitz-van der Waals component in vOCG method which represents dispersive interaction. However, the polar surface energy component (OW method) of mercapto template is about a third of cyano template which results in lower total surface energy for mercapto template compared to cyano template. In comparison with cyano template, the total surface energy of fluoro template is less than half. The dispersive component of fluoro surface is about half that of both cyano and mercapto templates. However, the polar component of fluoro surface is comparable with that of mercapto template. The trends are similar irrespective of the calculation methods employed in this study.

Functional head group

OW approach vOCG approach

𝜸𝜸𝑺𝑺𝒅𝒅 𝜸𝜸𝑺𝑺𝒑𝒑 𝜸𝜸𝑺𝑺 𝜸𝜸𝑺𝑺𝑳𝑳𝑳𝑳 𝜸𝜸𝑺𝑺+ 𝜸𝜸𝑺𝑺− 𝜸𝜸𝑺𝑺

Cyano (-CN) 38.0 14.2 52.2 41.9 0.7 9.3 47.0

Mercapto (-SH) 37.6 5.0 42.6 41.4 0.0 3.7 41.4

Fluoro (-CF3) 19.2 2.5 21.7 20.5 0.4 1.0 21.8

Table 4.5. Surface energy of templates calculated using Owens-Wendt (OW) approach and acid-base (vOCG) approach (values in mJ/m2).

It is to be acknowledged that the contact angle values on the control templates (clean glass surface) were not used for calculating their surface energy value. The probe liquids, specifically water wets the control surface completely resulting in very low contact angle values below 8 °. The accuracy of the image fitting methodology used for establishing the contact angle values using the software used in this analysis is arguable. In addition, due to the very low contact angle of water, the needle used for liquid injection to the advancing droplet interferes with the droplet shape, thus further affecting the results. Hence the surface energy values of the control templates are not computed in this section. From available references, clean glass surfaces are expected to have hydroxyl groups on the surface and exhibit high surface energy value >70 mJ/m2 _{as reported by Yongan Peter (2007) or 150-300} mJ/m2 _{as reported by Fisher (1948), specifically high polar surface energy} component.

Another aspect of the contact angle analysis that is to be discussed is the seemingly lower contact angle of fluoro functionalised template surface. Very high contact angle of water in the range of about 120 ° has been reported with fluorinated layer (Zisman, 1964). Low contact angle values could be attributed to patchy or incomplete surface coverage of the silane. Nonetheless, it is to be noted that such high values are reported in studies involving highly ordered SAMs with high fluorine content. However, the functional layer in our experiments consists of trifluoropropyl trimethoxy silane and the functionalised layer is not expected to be orderly packed when compared to that of SAM surfaces. Also, contact angle values in the range of 90 ° have been reported specifically with this silane (Owen & Williams, 1991;

Thomason, 2009). Hence it would be unable to conclude if the fluorinated surface layer is patchy from the obtained contact angle value.

To sum up the results of surface energy calculation from advancing contact angle data, the total surface energy of the template are in the order cyano > mercapto > fluoro. In case of dispersive component, the templates follow the order cyano ≈ mercapto > fluoro. For polar surface energy component, the order is cyano > mercapto ≈ fluoro.