Nanocelluloses are emerging as natural materials with favourable properties for coating industry and can be applied by state-of-the-art spraying technology. While additional functionalities are commonly introduced through chemical modification, the surface microstructuring of nanocellulose coatings with high throughput methods remains unexplored. Here, a femtosecond laser is used for texturing spray-coated coatings made of cellulose nanofibrils (CNF) or cellulose nanocrystals (CNC). For coating thickness of 1.5 to 8 μm, processing limits were determined with maximum ablation energy linearly increasing with coating thickness and minimum ablation energy decreasing or increasing depending on the apparent coating density. Within applicable processing window of pulse rate and power setting, the operational ranges were determined for creating one-dimensional and two-dimensional surface patterns, requiring a higher laser energy for CNC compared to CNF coatings and yielding thinnest possible resolved patterns of 17 μm as determined by the laser spot diameter. The laser ablation under low energy corresponds to an increase in surface roughness and intensifies surface hydrophilicity, while the line patterns are able to pin water droplets with rising water contact angles up to 90°. Present feasibility study opens future possibilities for managing surface properties of nanocellulose coatings in applications where tuning of surface hydrophilicity is required.

Laser microstructuring has been studied extensively in the last decades due to its versatile, contactless processing and outstanding precision and structure quality on a wide range of materials. A limitation of the approach has been identified in the utilization of high average laser powers, with scanner movement fundamentally limited by laws of inertia. In this work, we apply a nanosecond UV laser working in an intrinsic pulse-on-demand mode, ensuring maximal utilization of the fastest commercially available galvanometric scanners at scanning speeds from 0 to 20 m/s. The effects of high-frequency pulse-on-demand operation were analyzed in terms of processing speeds, ablation efficiency, resulting surface quality, repeatability, and precision of the approach. Additionally, laser pulse duration was varied in single-digit nanosecond pulse durations and applied to high throughput microstructuring. We studied the effects of scanning speed on pulse-on-demand operation, single- and multipass laser percussion drilling performance, surface structuring of sensitive materials, and ablation efficiency for pulse durations in the range of 1-4 ns. We confirmed the pulse-on-demand operation suitability for microstructuring for a range of frequencies from below 1 kHz to 1.0 MHz with 5 ns timing precision and identified the scanners as the limiting factor even at full utilization. The ablation efficiency was improved with longer pulse durations, but structure quality degraded.

Incidents can occur when handling energetic materials (EMs) due to their sensitivity to external stimuli. Mechanical (friction, impact) and electrical (electrostatic discharge (ESD)) stimuli can trigger involuntary ignition of EMs. Nanothermites, defined as highly reactive mixtures of a metal and a metal oxide, show interesting reactive properties (high temperature/amount of heat). However, their extreme sensitivity to ESD is a significant drawback in their development. With a sensitivity threshold of lower than a millijoule and considering the human body capacity discharge is a few tens of millijoules, the handling of such energetic mixtures is extremely hazardous. ESD desensitization is therefore of crucial importance for the use of these materials. To achieve this goal, polypyrrole (PPy) conductive polymer was used as an additive within an Al/SnO2 energetic formulation. This polymer is able to easily conduct the electrostatic charges, which is useful to avoid an ignition after a spark stimulus. PPy was added to the nanothermite through the elaboration of SnO2-PPy composites. Delaying the SnO2 introduction time during pyrrole\'s polymerization (t = 0, 1, 24 h) changed the microstructures of the composites. The various SnO2-PPy composites highlighted that the additive\'s distribution within the composite is a key component for the modulation of ESD sensitivity. For example, this threshold is higher for a nanothermite formulated with the composite elaborated at t = 0 h (96.5 mJ with 7.5 vol % of polymer) than a composition based on the composite at t = 24 h (16.9 mJ with 8.2 vol % of polymer). Meanwhile, the reactive properties are decreased. The loss of reactivity (e.g. combustion speed) was explained by the thermal insulating property of the additive. Overall, the aim of this study is to help in the understanding of ESD desensitization of nanothermites in order to make them safer for operators and adapted to the required applications.

Zero thermal expansion (ZTE) composites are typically designed by combining positive thermal expansion (PTE) with negative thermal expansion (NTE) materials acting as compensators and have many diverse applications, including in high-precision instrumentation and biomedical devices. La(Fe1-x,Six)13-based compounds display several remarkable properties, such as giant magnetocaloric effect and very large NTE at room temperature. Both are linked via strong magnetovolume coupling, which leads to sharp magnetic and volume changes occurring simultaneously across first-order phase transitions; the abrupt nature of these changes makes them unsuitable as thermal expansion compensators. To make these materials more useful practically, the mechanisms controlling the temperature over which this transition occurs and the magnitude of contraction need to be controlled. In this work, ball-milling was used to decrease particles and crystallite sizes and increase the strain in LaFe11.9Mn0.27Si1.29Hx alloys. Such size and strain tuning effectively broadened the temperature over which this transition occurs. The material\'s NTE operational temperature window was expanded, and its peak was suppressed by up to 85%. This work demonstrates that induced strain is the key mechanism controlling these materials\' phase transitions. This allows the optimization of their thermal expansion toward room-temperature ZTE applications.

Photoembossing is a powerful photolithographic technique to prepare surface relief structures relying on polymerization-induced diffusion in a solventless development step. Conveniently, surface patterns are formed by two or more interfering laser beams without the need for a lithographic mask. The use of nanosecond pulsed light-based interference lithography strengthens the pattern resolution through the absence of vibrational line pattern distortions. Typically, a conventional photoembossing protocol consists of an exposure step at room temperature that is followed by a thermal development step at high temperature. In this work, we explore the possibility to perform the pulsed holographic exposure directly at the development temperature. The surface relief structures generated using this modified photoembossing protocol are compared with those generated using the conventional one. Importantly, the enhancement of surface relief height has been observed by exposing the samples directly at the development temperature, reaching approximately double relief heights when compared to samples obtained using the conventional protocol. Advantageously, the light dose needed to reach the optimum height and the amount of photoinitiator can be substantially reduced in this modified protocol, demonstrating it to be a more efficient process for surface relief generation in photopolymers. Kidney epithelial cell alignment studies on substrates with relief-height optimized structures generated using the two described protocols demonstrate improved cell alignment in samples generated with exposure directly at the development temperature, highlighting the relevance of the height enhancement reached by this method. Although cell alignment is well-known to be enhanced by increasing the relief height of the polymeric grating, our work demonstrates nano-second laser interference photoembossing as a powerful tool to easily prepare polymeric gratings with tunable topography in the range of interest for fundamental cell alignment studies.

In numerous fields such as aerospace, the environment, and energy supply, ice generation and accretion represent a severe issue. For this reason, numerous methods have been developed for ice formation to be delayed and/or to inhibit ice adhesion to the substrates. Among them, laser micro/nanostructuring of surfaces aiming to obtain superhydrophobic behavior has been taken as a starting point for engineering substrates with anti-icing properties. In this review article, the key concept of surface wettability and its relationship with anti-icing is discussed. Furthermore, a comprehensive overview of the laser strategies to obtain superhydrophobic surfaces with anti-icing behavior is provided, from direct laser writing (DLW) to laser-induced periodic surface structuring (LIPSS), and direct laser interference patterning (DLIP). Micro-/nano-texturing of several materials is reviewed, from aluminum alloys to polymeric substrates.

The surfaces of animals, plants and abiotic structures are not only important for organismal survival, but they have also inspired countless biomimetic and industrial applications. Additionally, the surfaces of animals and plants exhibit an unprecedented level of diversity, and animals often move on the surface of plants. Replicating these surfaces offers a number of advantages, such as preserving a surface that is likely to degrade over time, controlling for non-structural aspects of surfaces, such as compliance and chemistry, and being able to produce large areas of a small surface. In this paper, we compare three replication techniques among a number of species of plants, a technical surface and a rock. We then use two model parameters (cross-covariance function ratio and relative topography difference) to develop a unique method for quantitatively evaluating the quality of the replication. Finally, we outline future directions that can employ highly accurate surface replications, including ecological and evolutionary studies, biomechanical experiments, industrial applications and improving haptic properties of bioinspired surfaces. The recent advances associated with surface replication and imaging technology have formed a foundation on which to incorporate surface information into biological sciences and to improve industrial and biomimetic applications. This article is part of the theme issue \'Bioinspired materials and surfaces for green science and technology\'.

Bacterial cellulose (BC)⁻gelatin (GEL) membranes were processed by successive periodate oxidation and a freeze-thawing/carbodiimide crosslinking procedure, first facilitating a Schiff-base reaction among respective aldehyde and hydroxyl groups, and later GEL stabilization and microstructuring. The formation of highly microporous structures within the GEL portion, with significant differences between bottom and top, was elucidated, and pores in the 27.6 ± 3 µm⁻108 ± 5 µm range were generated, exceeding the threshold value of ~10 µm sufficient for cell trafficking. During a relatively short (6 h) exhaustion procedure in supersaturated simulated body fluid solution, the membranes accommodated the combination of biologically relevant minerals, i.e., flake-like octacalcium phosphate (OCP) and (amorphous) apatite, onto their surface, forming a membrane with intensive swelling (650⁻1650%) and up to 90% weight loss in a 4-week period. The membranes´ 6-day eluates did not evoke any cytotoxic effects toward human fibroblast, MRC-5 cells. The same type of cells retained their morphology in direct contact with the membrane, attaching to the GEL porous site, while not attaching to the GEL thin-coated BC side, most probably due to combined, ablation effect of dominant β-sheet conformation and carbodiimide crosslinking. Together with arrested proliferation through the BC side, the membranes demonstrated beneficial properties for potential guided tissue regeneration (GTR) applications.

The metal-organic framework (MOF) HKUST-1 was employed as an interaction matrix for fundamental loading studies of anthraquinone dyes. Chosen dyes were alizarin (A), alizarin S (AS), disperse blue 1 (B1), disperse blue 3 (B3), disperse blue 56 (B56) and purpurin (P). All materials were characterized by XRD, FTIR, TGA and SEM. Hence the interaction of dyes with the framework was characterized by theoretical-experimental differential analysis. One-pot loading strategy resulted in more efficient scavenging of dyes, and reached 100 % for B56 using 50 mg L-1 . SEM revealed important microstructural changes, the smaller crystals ranged 0.8-3 μm in size and almost all composite sizes were from this to higher values, reaching 70 μm, with varying shapes. Two composites were larger in size range (about 2500-1000 μm), and were shaped as rods, octahedrons and coffin lids. Indeed, the microstructure could be modulated depending on preparation conditions and type of loaded dye. For the higher loading series, N2 adsorption and XPS experiments were carried on to further evidence dye-MOF interactions. Ab initio prediction of structural properties for A@HKUST-1 and P@HKUST-1 were obtained by means of solid-state CRYSTAL14 code at the PBE0 level of theory. Computed findings evidenced two O→Cu coordinative bonds, one from O-ketone and the other from O-phenolate moiety as main interactions towards CuNET centers.

It is demonstrated that the crystal size of small-molecule organic semiconductors can be controlled during solution shearing by tuning the shape and dimensions of the micropillars on the blade. Increasing the size and spacing of the rectangular pillars increases the crystal size, resulting in higher thin-film mobility. This phenomenon is attributed as the microstructure changing the degree and density of the meniscus line curvature, thereby controlling the nucleation process. The use of allylhybridpolycarbosilane (AHPCS), an inorganic polymer, is also demonstrated as the microstructured blade for solution shearing, which has high resistance to organic solvents, can easily be microstructured via molding, and is flexible and durable. Finally, it is shown that solution shearing can be performed on a curved surface using a curved blade. These demonstrations bring solution shearing closer to industrial applications and expand its applicability to various printed flexible electronics.