Evaluation of Structural and Compositional Changes of a Model Monoaromatic Hydrocarbon in a Benchtop Hydrocracker Using GC, FTIR, and NMR Spectroscopy.

Hydrogenation is a catalytic process that has the potential to facilitate sustainable chemical production. In this work, a model monoaromatic hydrocarbon, phenyldodecane (PDD), comprising an aromatic ring with a long aliphatic side chain has been chosen as representative of a typical species involved in hydrogenation and hydrocracked at a high pressure and temperature over a platinum catalyst in a bespoke benchtop mini-reactor. Gas chromatography-mass spectrometry (GC-MS), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy were employed to analyze the changes that took place after hydrocracking for different time periods. By combining the results from these sensitive spectroscopic tools, it was found that along with the saturation of the aromatic ring of PDD by hydrogen addition, new molecules were formed via ring opening and catalytic cracking. For comparison purposes, the spectra of the samples post hydrogenation were compared with those of cyclohexylnonadecane (CHND), which has a saturated six-membered ring and a long aliphatic tail.

Probing the Nanoscale Heterogeneous Mixing in a High-Performance Polymer Blend.

The blend of polyetheretherketone (PEEK) and polybenzimidazole (PBI) produces a high-performance blend (PPB) that is a potential replacement material in several industries due to its high temperature stability and desirable tribological properties. Understanding the nanoscale structure and interface of the two domains of the blend is critical for elucidating the origin of these desirable properties. Whilst achieving the physical characterisation of the domain structures is relatively uncomplicated, the elucidation of structures at the interface presents a significant experimental challenge. In this work, we combine atomic force microscopy (AFM) with an IR laser (AFM-IR) and thermal cantilever probes (nanoTA) to gain insights into the chemical heterogeneity and extent of mixing within the blend structure for the first time. The AFM-IR and nanoTA measurements show that domains in the blend are compositionally different from those of the pure PEEK and PBI polymers, with significant variations observed in a transition region several microns wide in proximity to domain boundary. This strongly points to physical mixing of the two components on a molecular scale at the interface. The versatility intrinsic to the combined methodology employed in this work provides nano- and microscale chemical information that can be used to understand the link between properties of different length scales across a wide range of materials.

Liquid repellency enhancement through flexible microstructures.

Artificial liquid-repellent surfaces have attracted substantial scientific and industrial attention with a focus on creating functional topological features; however, the role of the underlying structures has been overlooked. Recent developments in micro-nanofabrication allow us now to construct a skin-muscle type system combining interfacial liquid repellence atop a mechanically functional structure. Specifically, we design surfaces comprising bioinspired, mushroom-like repelling heads and spring-like flexible supports, which are realized by three-dimensional direct laser lithography. The flexible supports elevate liquid repellency by resisting droplet impalement and reducing contact time. This, previously unknown, use of spring-like flexible supports to enhance liquid repellency provides an excellent level of control over droplet manipulation. Moreover, this extends repellent microstructure research from statics to dynamics and is envisioned to yield functionalities and possibilities by linking functional surfaces and mechanical metamaterials.

Self-Compensating Liquid-Repellent Surfaces with Stratified Morphology.

Artificial liquid-repellent surfaces have recently attracted vast scientific attention; however, achieving mechanical robustness remains a formidable challenge before industrialization can be realized. To this end, inspired by plateaus in geological landscapes, a self-compensating strategy is developed to pave the way for the synthesis of durable repellent surfaces. This self-compensating surface comprises tall hydrophobic structural elements, which can repel liquid droplets. When these elements are damaged, they expose shorter structural elements that also suspend the droplets and thus preserve interfacial repellency. An example of this plateau-inspired stratified surface was created by three-dimensional (3D) direct laser lithography micro-nano fabrication. Even after being subjected to serious frictional damage, it maintained static repellency to water with a contact angle above 147° and was simultaneously able to endure high pressures arising from droplet impacts. Extending the scope of nature-inspired functional surfaces from conventional biomimetics to geological landscapes, this work demonstrates that the plateau-inspired self-compensating strategy can provide an unprecedented level of robustness in terms of sustained liquid repellency.

Three-Dimensional Printed Surfaces Inspired by Bi-Gaussian Stratified Plateaus.

Wettability of artificial surfaces is attracting increasing attention for its relevant technological applications. Functional performance is often achieved by mimicking the topographical structures found in natural flora and fauna; however, surface attributes inspired by geological landscapes have so far escaped attention. We reproduced a stratified morphology of plateaus with a bi-Gaussian height distribution using a three-dimensional direct laser lithography. The plateau-inspired artificial surface exhibits a hydrophobic behavior even if fabricated from a hydrophilic material, giving rise to a new wetting mechanism that divides the well-known macroscopic Wenzel and Cassie states into four substates. We have also successfully applied the plateau-inspired structure to droplet manipulation.

Bi-Gaussian Stratified Wetting Model on Rough Surfaces.

Wetting mechanisms on rough surfaces were understood from either a monolayer or a multiscale perspective. However, it has recently been shown that the bi-Gaussian stratified nature of real surfaces should be accounted for when modeling mechanisms of lubrication, sealing, contact, friction, acoustic emission, and manufacture. In this work, a model combining Wenzel and Cassie theories was put forward to predict the static contact angle of a droplet on a bi-Gaussian stratified surface. The model was initially applied to numerically simulated surfaces and subsequently demonstrated on hydrophilic steel and hydrophobic self-assembled monolayer specimens with preset bi-Gaussian stratified topographies. In the Wenzel state, both the upper and the lower surface components are fully wetted. In the Cassie state, the upper component is still completely wetted, while the lower component serves as gas traps and reservoirs. By this model, wetting evolution was assessed, and the existence of different wetting states and potential state transitions was predicted.