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Kumar Nanjundiah¹, Ali Dhinojwala

¹Department of Polymer Science, The University of Akron , Akron, Ohio 44325, United States.

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Summary

Confinement of linear alkanes between elastomers and sapphire lowers their melting points. This melting point depression depends on alkane chain length and confinement thickness, impacting soft material interfaces.

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Area of Science:

Materials Science
Physical Chemistry
Surface Science

Background:

Small molecules act as lubricants and plasticizers, but their interfacial behavior and property changes under confinement are poorly understood.
Previous work showed differences in crystal structure for confined versus unconfined pentadecane on sapphire.
Understanding interfacial properties is crucial for soft elastomeric materials.

Purpose of the Study:

To investigate the melting and freezing behavior of linear alkanes confined between poly(dimethylsiloxane) (PDMS) elastomers and sapphire.
To determine how confinement affects the transition temperatures (melting temperature, Tm) of these alkanes.
To model the observed melting point depression and relate it to confinement parameters.

Main Methods:

Utilized surface-sensitive infrared-visible sum-frequency-generation spectroscopy (SFG) to study interfacial alkanes.
Investigated alkanes confined within nanometer-thick interfacial regions between swollen PDMS elastomers and sapphire.
Employed differential scanning calorimetry (DSC) for PDMS elastomer analysis.

Main Results:

Confined alkanes exhibited a depression in melting temperature (Tm) compared to bulk alkanes.
The extent of Tm depression was dependent on alkane chain length, being most pronounced for 19-unit alkanes.
DSC results showed a broad distribution of melting points within the PDMS network.

Conclusions:

The melting temperature depression of confined alkanes is linked to confinement thickness, modeled using Flory-Rehner and Gibbs-Thomson theories.
Findings provide insights into friction and adhesion mechanisms in soft elastomeric materials.
This study elucidates the effects of confinement on molecular behavior at solid-solid interfaces.