Substrate Properties Research Articles

Drill cuttings from oil exploration improve properties of substrate and growth of Ipê-branco ( Tabebuia roseoalba ) seedlings

ABSTRACT More information is needed on the potential of using drill cuttings (crushed rocks) from the oil industry in agriculture and forestry. An experiment in forest nursery was carried out to evaluate the influence of substrates formulated from onshore gravel on characteristics of Ipê-branco (Tabebuia roseoalba) seedlings (i.e., growth, quality, and nutrition). We used five gravimetric proportions of gravel from drill cuttings mixed with Pinus-bark - commercial substrate (Mecplant® Florestal 3): control with only commercial substrate and zero gravel (G0), 2.5 % gravel (G2.5), 5 % gravel (G5), 7.5 % gravel (G7.5), and 10 % gravel (G10). In general, high proportion of drill cuttings increases density and decrease current moisture and total porosity of the formulated substrates. The drill cuttings proportions G2.5, G5 and G7.5 significantly contributed to the available water and readily available water in these substrates, with percentage values ranging 23 – 30 % higher than the G10 substrate. Increasing the gravel proportion generally resulted in increased pH levels, P, Na, K and metals (Cu, Fe, Ni, Mn, Cd, Zn, Cr and Pb), except for Ca and Mg nutrients that decreased. Heavy metal contents in all substrates did not exceed the permissible values in legal standards. The G2.5 and G5 substrates increased by 20 % approximately the stem diameter and height of seedlings, and G2.5 proportion also affected the root dry mass and Dickson quality index, with values two times higher than G0 substrate. Multivariate analysis proved suitable as a complementary approach to evaluate the seedling quality. Drilling cuttings addition, in general, increased the accumulation of nutrients and heavy metals of the Ipê-branco seedlings, and G2.5 and G5 substrates provided the greatest accumulation of the nutrients P, Ca, Pb and Zn in the shoot, while G2.5 proportion contributed with higher accumulation of N, Ca, Fe, Cr, Mn and Pb in the root. Adding drill cuttings as a conditioning component of the substrate at 2.5 and 5 % proportions is a viable alternative for using this residue to produce high-quality Tabebuia roseoalba seedling.

Unspecific Peroxygenase Catalyzes Selective Remote‐Site Functionalizations

AbstractWe describe the discovery of an unspecific peroxygenase (UPO) variant that catalyzes the remote‐site functionalization of halogenated and unsaturated hydrocarbons with high catalytic site‐specificity. UPOs are fungal heme‐thiolate biocatalysts with wide‐ranging oxidative activities, including C─H bond oxygenation, usually with limited regioselectivity. We describe here a wild‐type MroUPO, newly isolated in high yield from a previously uncharacterized strain of Marasmius rotula. This variant, MroUPO‐TN, catalyzes the selective oxygenation of a range of haloalkanes, cyclic haloalkanes and cyclic olefins to generate useful remote‐site haloketones. The regioselectivity for eight‐membered rings reaches 99% with significant enantiomeric excess. Mechanistic studies performed with deuterated substrates and 18O‐labeling experiments have revealed a synergy between intrinsic substrate properties and the highly aliphatic, heme active site. The observed selectivity offers routes to new and useful, bifunctional synthons and pharmacophores, thus providing practical ways to employ these natural and environmentally benign biocatalysts.

Growing Vigorous Potato Seedlings in Plug Trays

AbstractRaising vigorous and healthy potato seedlings from hybrid true potato seeds (TPS) under nursery conditions is critical for ease of field transplanting and seedling crop establishment as well as for a productive seed or ware crop. The use of plugs in seedling production systems is an important technique utilised to ease transplanting of seedlings and refine seedling production in seedling nurseries. While holding multiple advantages over other transplant production systems, multiple factors still influence the success of seedling production in plug trays. In this study, we explore the effects of substrate properties, type and volume; watering intervals; and nitrogen (N) and phosphorus (P) levels in nutrient solution on seedling vigour attributes in potato seedlings grown in plug trays under climate room conditions. The choice of substrate strongly influenced seedling attributes with more favourable performance in substrates with higher water holding capacity. Increasing plug volume also enhanced seedling attributes including dry biomass, leaf area and root to shoot ratios such that seedling performance was best in plug volumes > 22.5 cm3. A watering schedule with a high frequency was more favourable considering that longer intervals between watering events led to significant declines in seedling attributes. While the effects of increased P in solution were not conclusive, depending on genotype, increasing N in solution led to enhanced seedling attributes, with a nutrient sufficiency met at 200 mg L−1 N in solution. These findings further contribute to the current knowledge on factors influencing success in seedling production of potato seedlings developed from hybrid true potato seeds.

Anomalous CatalyticPerformance on Non-Active-Site Carbon Substrate.

Carbon-based nanomaterials are gaining attention in electrocatalysis. This study investigates the inherent nitrate reduction activity (NO3RR) of commercial carbon paper as a substrate. Results showed that carbon paper, without additional catalysts, achieved approximately 80.42% NH3Faradaic efficiency (FE) at -2.1 V vs. Hg/HgO in alkaline conditions, 83.51% NH3FE at -1.9 V vs. Ag/AgCl in neutral conditions, and 14.53% NH3FE at -1.9 V vs. MSE in acidic conditions. Density Functional Theory (DFT) calculations revealed energy barriers of 2.66 eV, 0.95 eV, and 1.37 eV, respectively. Molecular physisorption on the carbon paper surface generates an induced electric field, promoting charge transfer between the carbon paper and the adsorbed molecules, thus enhancing the activity of the carbon paper. These findings highlight the importance of considering the intrinsic catalytic properties of carbon substrates in catalyst design and evaluation, as overlooking these properties can lead to inaccurate performance assessments. This study emphasizes the need for a comprehensive approach to optimize catalytic systems.

On the Role of Substrate in Hydroxyapatite Coating Formation by Cold Spray

The deposition of agglomerated hydroxyapatite (HAp) powders by low-pressure cold spray has been a topic of interest in recent years. Key parameters influencing the deposition of HAp powders include particle morphology and impact kinetic energy. This work examines the deposition of HAp powders on various metal surfaces to assess the impact of substrate properties on the formation of HAp deposits via cold spray. The substrates studied here encompass metals with varying hardness and thermal conductivities, including Al6061, Inconel alloy 625, AISI 316 stainless steel, H13 tool steel, Ti6Al4V, and AZ31 alloy. Single-track experiments offer insights into the initial interactions between HAp particles and different substrate surfaces. In this study, the results indicate that the ductility of the substrate may enhance HAp particle deposition only at the first deposition stages where substrate/particle interaction is the most critical factor for deposition. Features on the substrate associated with the first deposition sprayed layer include localized substrate deformation and the formation of clusters of HAp agglomerates, which aid in HAp deposition. Furthermore, after multiple spraying passes on the various metallic surfaces, deposition efficiency was significantly reduced when the build-up process of HAp coatings shifted from ceramic/metal to ceramic/ceramic interactions. Overall, this study achieved agglomerated HAp deposits with high deposition efficiencies (30–60%) through single-track experiments and resulted in the preparation of HAp coatings on various substrates with thickness values ranging from 24 to 53 µm. These coatings exhibited bioactive behavior in simulated body fluid.

Preparation and Application of Two-Dimensional Ta4C3 MXene/Gold Nanostar Composite SERS Substrates for Thiram Detection.

Surface-enhanced Raman scattering (SERS) is a novel spectroscopic technique that enables the identification of analytes through analysis of their unique chemical signatures. Its high sensitivity, specificity, and rapid response make it a valuable tool in a range of fields, including biological detection, food safety, and environmental monitoring. However, traditional SERS nanoparticle substrates are susceptible to instability and agglomeration. In this study, Ta4C3 MXene/gold nanostar (AuNSs) hybrids were prepared as SERS substrates. By optimizing the experimental conditions of AuNSs, the optimal preparation method for the Ta4C3 MXene/AuNSs composite structure was identified. The addition of MXene to the Ta4C3 MXene/AuNSs hybrid substrates was found to enhance the sensitivity of the composite for Raman detection, as evaluated using 4-aminothiophenol (PATP) as a Raman molecule. This improvement in sensitivity is attributed to the enhanced electromagnetic properties of the hybrid substrates, which facilitate more efficient charge transfer and enhance the Raman scattering process. The limit of detection (LOD) of Ta4C3 MXene/AuNSs is 10-9 M for PATP and 10-7 M for thiram solutions. In addition, good reproducibility and spatial uniformity were obtained for the Raman signals of Ta4C3 MXene/AuNSs. Furthermore, Ta4C3 MXene/AuNSs were combined with filter paper to create paper-based SERS substrates that could be used for detection. By directly wiping the apple peel and subsequently detecting the thiram residues using Ta4C3 MXene/AuNSs, the level of detection of thiram residues on the peel surface was down to 7.8 ng/cm2.

Evaluation of the immune response of peripheral blood mononuclear cells cultured on Ti6Al4V-ELI polished or etched surfaces.

While titanium and its alloys exhibit excellent biocompatibility and corrosion resistance, their polished surfaces can hinder fast and effective osseointegration and other biological processes, such as angiogenesis, due to their inert and hydrophobic properties. Despite being commonly used for orthopedic implants, research focuses on developing surface treatments to improve osseointegration, promoting cell adhesion and proliferation, as well as increasing protein adsorption capacity. This study explores a chemical treatment intended for titanium-based implants that enhances tissue integration without compromising the mechanical properties of the Ti6Al4V substrate. However, recognizing that inflammation contributes to nearly half of early implant failures, we assessed the impact of this treatment on T-cell viability, cytokine production, and phenotype. Ti6Al4V with extra low interstitial (ELI) content discs were treated with hydrofluoric acid followed by a controlled oxidation step in hydrogen peroxide that creates a complex surface topography with micro- and nano-texture and modifies the chemistry of the surface oxide layer. The acid etched surface contains an abundance of hydroxyl groups, crucial for promoting bone growth and apatite precipitation, while also enabling further functionalization with biomolecules. While cell viability remained high in both groups, untreated discs triggered an increase in Th2 cells and a decrease of the Th17 subset. Furthermore, peripheral blood mononuclear cells exposed to untreated discs displayed a rise in various pro-inflammatory and anti-inflammatory cytokines compared to the control and treated groups. Conversely, the treated discs showed a similar profile to the control, both in terms of immune cell subset frequencies and cytokine secretion. The dysregulation of the cytokine profile upon contact with untreated Ti6Al4V-ELI discs, namely upregulation of IL-2 could be responsible for the decrease in Th17 frequency, and thus might contribute to implant-associated bacterial infection. Interestingly, the chemical treatment restores the immune response to levels comparable to the control condition, suggesting the treatment's potential to mitigate inflammation by enhancing biocompatibility.

Characterization of Silver Conductive Ink Screen-Printed Textile Circuits: Effects of Substrate, Mesh Density, and Overprinting

This study explores the intricate interaction between the properties of textile substrates and screen-printing parameters in shaping fabric circuits using silver conductive ink. Via analyzing key variables such as fabric type, mesh density, and the number of overprinted layers, the research revealed how the porous structure, large surface area, and fiber morphology of textile substrates influence ink absorption, ultimately enhancing the electrical connectivity of the printed circuits. Notably, the hydrophilic cotton staple fibers fabric effectively absorbed the conductive ink into the fabric substrate, demonstrating superior electrical performance compared with the hydrophobic polyester filament fabric after three overprinting, unlike the results observed after a single print. As mesh density decreased and the number of prints increased, the electrical resistance of the circuit gradually reduced, but ink bleeding on the fabric surface became more pronounced. Cotton fabric, via absorbing the ink deeply, exhibited less surface bleeding, while polyester fabric showed more noticeable ink spreading. These findings provide valuable insights for improving screen printing technology for textile circuits and contribute to the development of advanced fabric circuits that enhance the functionality of smart wearable technology.

Findings and perspectives of β-Ti alloys with biomedical applications: Exploring beyond biomechanical and biofunctional behaviour

Early implant failure and bone resorption may occur in load-bearing conditions as a result of stress shielding brought on by a mismatch in the bone-Ti-implant modulus. A review with a novel multidisciplinary perspective is proposed in this work, which considers recent developments of β-Titanium alloys and new trends in novel microstructures, processing techniques, properties of dense and porous substrates, as well as the relationship between all these aspects and performance in service, in terms of improved its biomechanical and bio-functional balance. In addition to highlighting several modern and historical uses for Ti alloys, this review covers many cutting-edge novel β-Ti alloys and uses that promise to exceed historical standards. Also, it deepens through several important properties of these alloys, including toxicity of alloying elements, phase stability, thermo-mechanical processing, heat treatment, surface, and stress-induced modifications. The stiffness, hardness, fatigue and wear resistance, corrosion behaviour, biocompatibility, and manufacturing and surface modification effects on these parameters are also emphasized. In-vitro and in-vivo assays have been added to highlight important aspects of bioactivity and antibacterial behaviour, and future significant research areas are suggested along with new techniques to ensure the successful clinical application of β-Ti alloys.

Charge‐Mediated Interactions Affect Enzymatic Reactions in Peptide Condensates

Abstract: Biomolecular condensates, formed through liquid‐liquid phase separation (LLPS), serve as enzymatic reaction centers in cells by increasing local concentrations of enzymes and substrates, thereby facilitating reaction kinetics and regulatory mechanisms. Inspired by these natural systems, synthetic condensates are being developed for diverse applications, including payload delivery, sensing, and as microreactors where enzymatic reaction kinetics can be modulated by factors like pH, viscosity, and enzyme‐substrate co‐localization. Here, we investigate how the physicochemical properties of enzymes and substrates influence condensate formation and function as microreactors. Focusing on cellulase and alkaline phosphatase, which differ in molecular weight and isoelectric point, we employed a minimalistic complex coacervation system of oppositely charged LLPS‐promoting peptides. Our findings show how electrostatic forces within condensates influence their role as microreactors. Specifically, the ability of condensates to encapsulate or exclude phosphatase and cellulase and their substrates, which is pivotal for the regulation of reaction kinetics, is determined by the enzyme surface charge, substrate charge, and condensate charge stoichiometry. These results highlight the potential of utilizing electrostatic forces within condensates to modulate enzymatic reactions, providing critical insights for developing synthetic condensates as microreactors in biotechnology and materials science.

An inhibitive system to mitigate the corrosion of AA2024-T3 in 3.5 wt% NaCl solution: Utilizing the synergistic effect of cerium cations and benzimidazole molecules

This study aims to improve the anti-corrosion protection performance of AA2024-T3 using the synergistic effect of organic and inorganic corrosion inhibitors in saline solution. Combining the Ce3+ cations and benzimidazole (BI) molecules was employed as the inhibitive system for the AA2024-T3. Electrochemical properties of the metallic substrate in the presence and absence of the inhibitive system were studied utilizing EIS, PD, and OCP techniques. In addition, GIXRD, ATR-FTIR, XPS, OM, FE-SEM/EDS, water contact angle, and AFM were hired to study the protection mechanism. Based on the results obtained, the inhibitive system has a synergistic effect in improving the anti-corrosion protection performance of AA2024-T3. The synergistic index for the Ce + BI system was calculated to be around 19. Also, the efficiency of the synergistic system in the simultaneous presence of Ce3+ cations and BI molecules as the corrosion inhibitor was 99.3 %, which is higher than that of other inhibitive systems. Finally, the surface analysis outcomes revealed that the inhibitive film forming on the samples' surface during the immersion of the sample in the saline solution in the presence of the inhibitive species is the main factor in boosting the anti-corrosion properties of the aluminum substrate.

Wrinkling of differentially growing bilayers with similar film and substrate moduli

Growth-induced surface wrinkling in constrained bilayers comprising a thin film attached to a thick substrate is a canonical model for understanding pattern formation in many biological systems. While the bilayer model has received much prior attention, the nonlinear behaviour for arrangements with similar film and substrate properties, or substrate growth that outpaces film growth, remains poorly understood. This paper therefore focuses on these cases in which the substrate’s elasticity dominates surface wrinkling. By combining analytical modelling and finite element simulations incorporating advanced path-following techniques, we characterise critical wrinkling states and explore the initial and advanced post-buckling behaviour for a wide range of film-to-substrate modulus and growth rate ratios. It is shown that the classical leading-order asymptotic expression for the critical strain is not of sufficient accuracy for film-to-substrate modulus ratios below 50, and higher order correction terms are presented. Leveraging a weakly nonlinear analytical model, we introduce a phase diagram categorising stable and unstable post-buckling regimes. Advanced path-following simulations are employed to unveil the evolution of wrinkling patterns, from initial sinusoidal instabilities to complex formations involving period doubling, quadrupling, and eventual surface creasing. These comprehensive phase diagrams, parameterised by film-to-substrate modulus and growth rate ratios, provide new insights into the rich dynamics of surface wrinkling. Finally, we demonstrate the existence of multi-stability in the advanced post-buckling regimes for bilayers experiencing substrate-dominated growth. This work contributes to the understanding of the mechanics underlying pattern formation in growing bilayers over the entire parameter regime, with potential implications for explaining biological morphogenesis and informing the development of novel diagnostic tools and artificial flexible electronic skins.

Preparation and characterization of highly CO2 permeable and selective graphene oxide membranes by introducing gutter layers into porous substrates

Here, we present graphene oxide (GO)-based thin-film composite (TFC) membranes with enhanced CO2 separation performance using a surface-modified substrate for uniform GO depositions. We extensively characterized the surface properties of porous substrates to identify optimal conditions for universal and uniform GO selective layer. Our results reveal that incorporating polyvinylpyrrolidone (PVP) as a gutter layer is essential for achieving consistent and regular GO layer coating. As a result, the developed GO membranes demonstrate a CO2 permeance of 350 GPU, which is a ∼350 % improvement over the GO membranes without gutter layer, coupled with a higher selectivity for CO2/N2 and CO2/CH4 pairs. The results indicate the excellent potential for significantly enhanced CO2 separation performances with the development of suitable support membranes.

Effect of argon and nitrogen environments on the structure and properties of protective cermet coatings based on titanium borides obtained by electric arc surfacing

The aim of this work was to enhance the mechanical and tribological properties of an alpha titanium substrate by forming a protective cermet coating on its surface. In this study, protective cermet coatings based on titanium borides were prepared by electric arc surfacing in a protective environment. Two types of protective environment were investigated during the surfacing process: (i) inert (argon) and (ii) reactive (nitrogen). The characteristic zones of the deposited layer were established depending on the environment used, and the coating-substrate transition zone was thoroughly examined. It was demonstrated that the formation of the transition zone results from the mutual diffusion of the molten material of the electrode material and the substrate. For the first time, the formation of TiB2-TiN eutectic in the form of whiskers 4-20 μm wide and 100-300 μm long distributed in the matrix of the Ti(B,N)x solid solution was established when forming a protective cermet coating in a nitrogen environment. The presence of this TiB2-TiN eutectic led to a significant increase in the hardness of the coating, up to 4.4 times, from 350 to 1530 HV. Tribological tests of surfacing coatings were conducted, and both 2D and 3D profiles of the wear grooves are presented, providing insight into the wear mechanism. It was found that the wear resistance of the cermet coating obtained in a nitrogen environment increased by 5.2 times, while in an argon environment it increased by 3.1 times as compared to the substrate without the protective cermet coating. The results indicate the potential of the developed protective cermet coatings for use in abrasive operating conditions.

Effects of Time-Elapsed Bleaching on the Surface and Mechanical Properties of Dentin Substrate Using Hydrogen Peroxide-Free Nanohydroxyapatite Gel.

There is a critical need to address concerns surrounding the potential impact of bleaching gels specifically on the tooth substrate. Therefore, this laboratory investigation aimed to assess the impact of a hydrogen peroxide (HP)-free bleaching (HiSmileTM) in comparison to an HP-based bleaching (Opalescence RegularTM) on the surface and mechanical characteristics of tooth substrate. Sixty sound human premolar teeth were sectioned to produce dentin fragments and divided into two primary groups based on the bleaching agent used. Each group was subdivided into three subgroups (n = 10) per distinct bleaching regimens: (T1) fragments underwent a 7-day immersion in distilled water at 37°C without any bleaching treatment, (T2) fragments underwent a 7-day immersion in distilled water at 37°C, with the application of bleaching gel occurring on the seventh day for 10minutes, and (T3) fragments underwent a bleaching regimen for seven consecutive days, each session lasting for 10minutes. The initial and final evaluations of surface roughness, nano-hardness, and elastic modulus were performed. Following the bleaching regimens of T3, a composite stub was fabricated on the dentin fragments for the shear bond strength (SBS) test. Statistical testing was accomplished using the analysis of variance (P < 0.05). HP-based bleaching gel showed significant differences between measurement intervals in surface roughness, elastic modulus, and SBS parameters (P < 0.05). In contrast, HP-free bleaching gel showed insignificant differences within the group (P > 0.05). The SBS between dentin-composite was significantly affected with the use of HP-based bleaching gel, while HP-free bleaching gel showed insignificant difference between measurement intervals. The qualitative validation of the treatment's impact was further demonstrated using the scanning electron microscopy. The findings suggest that the bonding stability of composite restorations to dentin may be compromised after bleaching with an HP-based gel, whereas immediate bonding procedures can be safely conducted following the application of an HP-free bleaching gel.

Abnormal Magnetic Phase Transition in Mixed-Phase (110)-Oriented FeRh Films on Al2O3 Substrates via the Anomalous Nernst Effect.

Iron rhodium (FeRh) undergoes a first-orderanti-ferromagnetic to ferromagnetic phase transition above its Curie temperature. By measuring the anomalous Nernst effect (ANE) in (110)-oriented FeRh films on Al2O3 substrates, the ANE thermopower over a temperature range of 100-350 K is observed, with similar magnetic transport behaviors observed for in-plane magnetization (IM) and out-of-plane magnetization (PM) configurations. The temperature-dependent magnetization-magnetic field strength (M-H) curves revealed that the ANE voltage is proportional to the magnetization of the material, but additional features magnetic textures not shown in the M-H curves remained intractable. In particular, a sign reversal occurred for the ANE thermopower signal near zero field in the mixed-magnetic-phase films at low temperatures, which is attributed to the diamagnetic properties of the Al2O3 substrate. Finite element method simulations associated with the Heisenberg spin model and Landau-Lifshitz-Gilbert equation strongly supported the abnormal heat transport behavior from the Al2O3 substrate during the experimentally observed magnetic phase transition for the IM and PM configurations. The results demonstrate that FeRh films on an Al2O3 substrate exhibit unusual behavior compared to other ferromagnetic materials, indicating their potential for use in novel applications associated with practical spintronics device design, neuromorphic computing, and magnetic memory.

Efficient perovskite light-emitting diodes on a flexible substrate.

The surface properties of target substrates are crucial for the in situ crystallization and growth of metal halide perovskite films fabricated by the anti-solvent method. In this work, a high-quality quasi-2D perovskite film with various-n phases is fabricated on the commonly used poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) by introducing a branched polyethylenimine (PEI) modifying layer. PEI suppresses the influence of acidic surface of the PEDOT:PSS and regulates the components of the perovskite film, increasing the proportion of large-n phases. Additionally, PEI reduces the formation of defects in perovskite films, leading to higher photoluminescence quantum efficiency and longer photoluminescence lifetime. Based on this high-quality perovskite film, a flexible light-emitting diode with an ultimate current efficiency of 63.2 cd/A is achieved, nearly twofold higher than that of the device (35.1 cd/A) without a PEI modifying layer.

Hydraulic Property Estimation of Green Roof Substrates from Soil Moisture Time Series

The adoption of green roofs is an effective practice for mitigating environmental issues in urban areas caused by extreme weather conditions. However, certain design aspects of green roofs, such as the characterization of the physical properties of their substrates, need a better understanding. This study proposes a simple method for estimating two hydraulic properties of green roof substrates based on the evolution of moisture during drying periods, or drydowns, where evaporative processes dominate: the weighted-mean diffusivity and the saturated hydraulic conductivity. Soil moisture was monitored using 12 in situ sensors from 2015 to 2020 in a study involving six different green roof plots composed of various mixtures of demolition-recycled aggregates and organic substrates. A universal parameterization for determining water diffusivity in soils was applied to estimate the weighted-mean hydraulic diffusivity. As a by-product, the saturated hydraulic conductivity was estimated from the evaluated diffusivity and the measured water retention data. The median values obtained for and range from 14.5 to 29.9 cm2d−1 and from 22 to 361 cmd−1, respectively. These values fall within the ranges reported by other research groups using direct measurement methods and supports the validity of Brutsaert’s model for green roof substrates. Furthermore, an increase in and a decrease in were observed as the percentage of recycled aggregates in the substrates increased, which could be considered for design purposes.

Human walking biomechanics on sand substrates of varying foot sinking depth.

Our current understanding of human gait is mostly based on studies using hard, level surfaces in a laboratory environment. However, humans navigate a wide range of different substrates every day, which incur varied demands on stability and efficiency. Several studies have shown that when walking on natural compliant substrates there is an increase in energy expenditure. However, these studies report variable changes to other aspects of gait such as muscle activity. Discrepancies between studies exist even within substrate types (e.g. sand), which suggests that relatively 'fine-scale' differences in substrate properties exert quantifiable influences on gait mechanics. In this study, we compare human walking mechanics on a range of sand substrates that vary in overall foot sinking depth. We demonstrate that variation in the overall sinking depth in sand is associated with statistically significant changes in joint angles and spatiotemporal variables in human walking but exerts relatively little influence on pendular energy recovery and muscle activations. Significant correlated changes between gait metrics are frequently recovered, suggesting a degree of coupled or mechanistic interaction in their variation within and across substrates. However, only walking speed (and its associated spatiotemporal variables) correlate frequently with absolute foot sinkage depth within individual sand substrates, but not across them. This suggests a causative relationship between walking speed and foot sinkage depth within individual sand substates is not coupled with systematic changes in joint kinematics and muscle activity in the same way as is observed across sand substrates.

How substrate surface area and surface curvature determine kinetics and titanate formation during non-hydrothermal alkali treatment of titanium microspheres

Titanium surface nanostructuring using alkali treatment gains significant attention in a wide range of fields, such as biomaterials, (photo)catalysis, (metal/ion) sorption, CO2 capture, electrochromism and sodium-ion batteries. Even though the physicochemical properties and application potentials of the surface nanostructures are fairly well understood, there is still debate about their exact formation mechanism, limiting knowledge based structural control through altered synthesis conditions. Moreover, this knowledge is largely focused on hydrothermal synthesis conditions, whereas non-hydrothermal conditions might provide benefits towards industrial application. Also the impact of substrate properties, rather than chemical reaction conditions, on the nanostructure formation is only limitedly reported in literature. This work reveals new fundamental knowledge of non-hydrothermal alkali treatment of titanium, using microspheres by implementing, for the first time, in-situ hydrogen measurement during alkali treatment in combination with the ex-situ determination of the sodium and oxygen content in the recovered alkali treated samples, providing critical information on the role of dissolution apart from the precipitation process. The effect of surface area and surface curvature on the dissolution and precipitation process, and the resulting impact on the physicochemical properties of the obtained titanate layer is studied. This shows the much larger impact on dissolution in contrast to precipitation, knowledge that is lacking in literature, but important when implementing alkali surface nanostructuring on complex (e.g. 3D printed) substrates, and considering the prospective shift from lab-scale to industry. The Ti dissolution step was found to be mainly controlled by the total surface area, while the rate determining step was found to be the titanate precipitation, not influenced by either surface area or particle size.The changes in oxygen content in the samples after transformation of titanate into TiO2 provided a novel method for its quantification. The microspheres were analysed chemically (Raman), structurally (XRD) and morphologically (SEM, MIP), screening the effect of surface area, particle size and reaction time on the growth behaviour of the titanate layer. The porous layer structurally corresponds to Na2Ti2O4(OH)2 for all evaluated conditions, with pores in the range of 10–600 nm. Increasing surface area and particle size results in local and non-uniform titanate growth, while titanate nanowire and strut formation between the microspheres were enhanced by reduced microsphere size and prolonged reaction times.