We are pleased to introduce the collection, 2022 Retrospective: Environmental Degradation of Materials. This collection aims to showcase original research and review-based papers on the most exciting developments of the past couple of years. The work presented here highlights the broad diversity of research performed across the section, and aims to put a spotlight on the main areas of interest. All research presented here seeks to display strong advances in theory, experiment, and methodology with applications to compelling problems. Authors are encouraged to showcase their most recent discoveries and to kickstart scientific discourse around them.

Southern University of Science and Technology

Istanbul Technical University

DECHEMA Forschungsinstitut (DFI)

Frontiers in Materials

Environmental Degradation of Materials

2022 Retrospective: Environmental Degradation of Materials

Polymeric multilayer films were prepared using a layer-by-layer (LBL) technique on glass surfaces, by repeated and sequential dipping into dilute aqueous solutions of various combinations of water-soluble polyanions (polyacrylic acid (PAA)), polycations (polyallylamine hydrochloride (PAH) or chitosan (CS)), with bi-functional water-soluble cationic azo dyes bismark brown R bismarck brown red or bismark brown Y (BBY), or anionic azo dyes allura red (ALR) or amaranth (AMA), as ionic cross-linkers. The electrostatically-assembled ionically-paired films showed good long-term stability to dissolution, with no re-solubility in water. However, upon exposure to low power visible light under running water, the films photo-disassembled back to their water-soluble constituent components, via structural photo-isomerization of the azo ionic crosslinkers. The relative rate of the disassembly (RRD) of the films was established using UV-Vis spectroscopy, demonstrating that these assemblies can in principle represent fully recyclable, environmentally structurally degradable materials triggered by exposure to sunlight, with full recovery of starting components. A density functional theory treatment of the allura red azo dye rationalizes the geometrical isomerization mechanism of the photo-disassembly and provides insight into the energetics of the optically-induced structural changes that trigger the disassembly and recovery.

Polymeric multilayer films were prepared using a layer-by-layer (LBL) technique on glass surfaces, by repeated and sequential dipping into dilute aqueous solutions of various combinations of water-soluble polyanions (polyacrylic acid (PAA)), polycations (polyallylamine hydrochloride (PAH) or chitosan (CS)), with bi-functional water-soluble cationic azo dyes bismark brown R bismarck brown red or bismark brown Y (BBY), or anionic azo dyes allura red (ALR) or amaranth (AMA), as ionic cross-linkers. The electrostatically-assembled ionically-paired films showed good long-term stability to dissolution, with no re-solubility in water. However, upon exposure to low power visible light under running water, the films photo-disassembled back to their water-soluble constituent components, via structural photo-isomerization of the azo ionic crosslinkers. The relative rate of the disassembly (RRD) of the films was established using UV-Vis spectroscopy, demonstrating that these assemblies can in principle represent fully recyclable, environmentally structurally degradable materials triggered by exposure to sunlight, with full recovery of starting components. A density functional theory treatment of the allura red azo dye rationalizes the geometrical isomerization mechanism of the photo-disassembly and provides insight into the energetics of the optically-induced structural changes that trigger the disassembly and recovery.

Azo dye polyelectrolyte multilayer films reversibly re-soluble with visible light

In this study, two kinds of Co–Ni-layer double hydroxide (LDH)/ZnO films were prepared with different morphologies by a simple electrochemical method. The properties of the films were investigated by SEM, XRD, UV–Vis DRS, XPS, and electrochemical techniques. It was found that Co–Ni-LDH-modified ZnO films exhibited excellent photocathodic properties in a scavenger-free environment. This is mainly due to the absorption of visible light by LDH, the formation of p–n heterojunction, and the depletion of photo-generated holes by the cycling process of Co (II)/Co (III). Compared with CoNi-LDH/ZnO nanorods, CoNi-LDH/ZnO nanoclusters showed better photocathodic protection performance and physical barrier effect. Under illumination conditions, the rough surface of ZnO nanoclusters and the deposition of a large amount of LDH can provide more photoelectrochemical active sites, thus improving the light absorption capacity and photocathodic protection performance of CoNi-LDH/ZnO nanoclusters. Under dark conditions, the physical barrier effect of CoNi-LDH/ZnO nanoclusters was also enhanced by the dense ZnO nanoclusters and thick CoNi-LDH layers.

In this study, two kinds of Co–Ni-layer double hydroxide (LDH)/ZnO films were prepared with different morphologies by a simple electrochemical method. The properties of the films were investigated by SEM, XRD, UV–Vis DRS, XPS, and electrochemical techniques. It was found that Co–Ni-LDH-modified ZnO films exhibited excellent photocathodic properties in a scavenger-free environment. This is mainly due to the absorption of visible light by LDH, the formation of p–n heterojunction, and the depletion of photo-generated holes by the cycling process of Co (II)/Co (III). Compared with CoNi-LDH/ZnO nanorods, CoNi-LDH/ZnO nanoclusters showed better photocathodic protection performance and physical barrier effect. Under illumination conditions, the rough surface of ZnO nanoclusters and the deposition of a large amount of LDH can provide more photoelectrochemical active sites, thus improving the light absorption capacity and photocathodic protection performance of CoNi-LDH/ZnO nanoclusters. Under dark conditions, the physical barrier effect of CoNi-LDH/ZnO nanoclusters was also enhanced by the dense ZnO nanoclusters and thick CoNi-LDH layers.

A Comparative Study of CoNi-LDH/ZnO Film for Photocathodic Protection Applications in the Marine Environment

Under operating conditions, alternated loading and fatigue are encountered, controlling the durability and safety of components and structures made of super duplex stainless steel (SDSS). In particular, the use of a cathodic protection (CP) system to protect the structure against corrosion can induce hydrogen charging of the SDSS. Thus, the aim of this study was to investigate the sensitivity of some industrial products made of SDSS 2507 (UNS S32750), without artificial thermal aging, under test conditions as close as possible to real environments. In situ fatigue tests under alternated 4-point bending conditions were conducted in natural seawater with and without CP. The fatigue behavior was evaluated as a function of environmental parameters, such as temperature, and material parameters, particularly the austenite spacing and microstructure around orbital welds by Tungsten Inert Gas (TIG) welding and stress concentrations, through the presence of surface defects. The fatigue life obtained in air or in seawater at the open circuit potential (OCP) was rather similar. Fatigue life enhancement was systematically observed under CP particularly in the range of low applied load, despite evidence of brittle failure on the fracture surfaces of samples tested under CP. The data suggest immunity of the SDSS to hydrogen embrittlement under the present experimental conditions of fatigue testing.

Under operating conditions, alternated loading and fatigue are encountered, controlling the durability and safety of components and structures made of super duplex stainless steel (SDSS). In particular, the use of a cathodic protection (CP) system to protect the structure against corrosion can induce hydrogen charging of the SDSS. Thus, the aim of this study was to investigate the sensitivity of some industrial products made of SDSS 2507 (UNS S32750), without artificial thermal aging, under test conditions as close as possible to real environments. In situ fatigue tests under alternated 4-point bending conditions were conducted in natural seawater with and without CP. The fatigue behavior was evaluated as a function of environmental parameters, such as temperature, and material parameters, particularly the austenite spacing and microstructure around orbital welds by Tungsten Inert Gas (TIG) welding and stress concentrations, through the presence of surface defects. The fatigue life obtained in air or in seawater at the open circuit potential (OCP) was rather similar. Fatigue life enhancement was systematically observed under CP particularly in the range of low applied load, despite evidence of brittle failure on the fracture surfaces of samples tested under CP. The data suggest immunity of the SDSS to hydrogen embrittlement under the present experimental conditions of fatigue testing.

Fatigue Behavior of Super Duplex Stainless Steel Exposed in Natural Seawater Under Cathodic Protection

The local lattice strain evolution during electrochemical hydrogen charging and mechanical loading in 25Cr-7Ni super duplex stainless steel were measured in-situ using synchrotron high-energy x-ray diffraction. Post-mortem electron backscattered diffraction analysis showed that the austenite phase underwent plastic deformation in the near-surface due to hydrogen-enhanced localized plasticity, where the ferrite phase experienced hardening. In bulk regions, the ferrite was the softer phase, and the austenite remained stiff. Digital image correlation of micrographs recorded, in-situ, during mechanical tensile testing revealed intensified plastic strain localization in the austenite phase, which eventually led to crack initiation. The absorption of hydrogen caused strain localization to occur primarily in austenite grains.

The local lattice strain evolution during electrochemical hydrogen charging and mechanical loading in 25Cr-7Ni super duplex stainless steel were measured in-situ using synchrotron high-energy x-ray diffraction. Post-mortem electron backscattered diffraction analysis showed that the austenite phase underwent plastic deformation in the near-surface due to hydrogen-enhanced localized plasticity, where the ferrite phase experienced hardening. In bulk regions, the ferrite was the softer phase, and the austenite remained stiff. Digital image correlation of micrographs recorded, in-situ, during mechanical tensile testing revealed intensified plastic strain localization in the austenite phase, which eventually led to crack initiation. The absorption of hydrogen caused strain localization to occur primarily in austenite grains.

Hydrogen-Induced Micro-Strain Evolution in Super Duplex Stainless Steel—Correlative High-Energy X-Ray Diffraction, Electron Backscattered Diffraction, and Digital Image Correlation