Surface Structure Research Articles

Characterization and Performance Analysis of TiO<sub>2</sub> Coated UHMWPE for Biomedical Applications

Ultra-high Molecular Weight Polyethylene (UHMWPE) is a highly versatile polymer known for its exceptional mechanical properties, however, its limited life as an implant material for Total Joint Replacement (TJR) necessitates surface modification to extend its lifespan. This study aims to enhance the surface properties of UHMWPE through application of ceramic coatings. Magnetron sputtering method was used to deposit thin film of white Titania (TiO2) on the material’s surface. To evaluate the surface characteristics, such as surface roughness, uniformity and structure, coated and uncoated samples were analyzed through Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and X-ray Diffraction Analysis (XRD). The material performance in relation to biological context was investigated through Contact Angle measurement. A comparative analysis of coated and uncoated samples was then performed. The coated samples showed better wettability compared to uncoated sample. This fact highlights the hydrophilic nature of film. The results of the coated UHMWPE suggest that this surface modification technique could significantly extend the lifespan of UHMWPE implants in TJR, potentially addressing the current limitations associated with their longevity.

Study on selective green leaching of rare earth elements from coal gangue using mechanochemical activation

This study proposes a sustainable method for the selective leaching of rare earth elements (REEs) from coal gangue. By combining 600 °C calcination, the addition of 5 % Fe2(SO4)3, and one hour of mechanical-chemical activation, we achieved a leaching efficiency of 65 % for REEs. This method alters the surface and crystalline structure of coal gangue, facilitating the release of rare earth phosphate minerals and the formation of water-soluble compounds (rare earth sulfates). Fe2(SO4)3 transforms into insoluble iron oxide, which immobilizes impurities and promotes the selective leaching of rare earth elements. Notably, during the leaching process, the leaching rates of aluminum (Al) and iron (Fe) were only 0.37 % and 1.27 %, respectively. Kinetic analysis indicates that this process follows a mixed reaction-controlled shrinking core model. This method effectively reduces the environmental risks associated with traditional acidic reagents, providing a sustainable pathway for the recovery of rare earth elements.

Regulating surface terminals and interlayer structure of Ti3C2Tx for superior NH3 sensing

MXene materials have exhibited potential in electrochemistry, particularly in gas sensing, due to their excellent conductivity, large specific surface area of layered materials, and unique functional groups. However, the gas sensing performance of intrinsic 2D MXene materials is often limited by their fluorine-containing terminals and interfacial structure. In this study, based on intrinsic Ti3C2Tx, we employed alkali treatment and annealing to prepare oxygen-rich Ti3C2(OH)x/Ti3C2Ox with expanded interlayer spacing, achieving enhanced gas sensing performance for NH3. The surface chemistry and structure of the sensing materials have been optimized through the synergistic regulation of MXene's unique surface terminations and the intercalation effect of layered materials. Compared to intrinsic Ti3C2Tx, the interlayer spacing of oxygen-rich Ti3C2(OH)x/Ti3C2Ox increased from 9.1 Å to 12.1 Å. The surface terminations of oxygen-rich Ti3C2(OH)x/Ti3C2Ox have been defluorinated and oxygenated. The maximum response value of oxygen-rich Ti3C2(OH)x/Ti3C2Ox to NH3 was 35.66, approximately twice that of the original Ti3C2Tx at an NH3 concentration of 200 ppm. DFT (Density functional theory) calculations and DRIFT (In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy) tests explained the interaction between the surface terminals and NH3, indicating good selectivity and sensitivity of oxygen-rich Ti3C2(OH)x/Ti3C2Ox to NH3. The results demonstrated that the synergistic effects of surface chemistry and structural engineering are crucial for MXene to optimize the electrochemical performance, particularly the gas sensing performance. This provides a feasible approach for the performance optimization of intrinsic MXene materials.

Dynamic Behavior of Pt Multimetallic Alloys for Active and Stable Propane Dehydrogenation Catalysts.

Improving the use of platinum in propane dehydrogenation catalysts is a crucial aspect to increasing the efficiency and sustainability of propylene production. A known and practiced strategy involves incorporating more abundant metals in supported platinum catalysts, increasing its activity and stability while decreasing the overall loading. Here, using colloidal techniques to control the size and composition of the active phase, we show that Pt/Cu alloy nanoparticles supported on alumina (Pt/Cu/Al2O3) displayed elevated rates for propane dehydrogenation at low temperature compared to a monometallic Pt/Al2O3 catalyst. We demonstrate that the enhanced catalytic activity is correlated with a higher surface Cu content and formation of a Pt-rich core and Cu-rich shell that isolates Pt sites and increases their intrinsic activity. However, rates declined on stream because of dynamic metal diffusion processes that led to a more uniform alloy structure. This transformation was only partially inhibited by adding excess hydrogen to the feed stream. Instead, cobalt was introduced to provide trimetallic Pt/Cu/Co catalysts with stabilized surface structure and stable activity and higher rates than the original Pt/Cu system. The structure-activity relationship insights in this work offer improved knowledge of propane dehydrogenation catalyst development featuring reduced Pt loadings and notable thermal stability for propylene production.

Observations of the Near‐Field Yellow River Plume, Multiple Fronts and Their Biogeochemical Effects

AbstractRiver plumes transport fresh water into the ocean, and exhibit intense convergent and turbulent processes in the frontal regions, ultimately influencing coastal ecosystems. Satellite images show multiple fronts can be generated in river plumes. Although some efforts have been done to study the generation of multiple fronts inside river plumes by theoretical, numerical modeling and laboratory methods, their generation mechanisms and effects on biogeochemical processes remain to be clarified through in situ observational evidence. In the present study, the near‐field Yellow River plume, multiple fronts and their biogeochemical effects are investigated through moored, shipboard, and remote sensing observations. Numerical model simulations are conducted to help study the tidal movement of the Yellow River plume. The results show that the near‐field Yellow River plume is generally advected back and forth in the east‒west direction under the effects of tidal currents. Following the plume leading front, a turbulent bore is observed to be generated and mix near‐surface water with low turbidity and high concentration of dissolved oxygen into the water column. Behind the turbulent bore, a series of subfronts with distances of O (∼100 m) are formed. The generation mechanisms of these subfronts are found to be associated with internal shear instabilities. Under the effects of cross‐front shear currents and vertical mixing near the subfronts, a three‐layer structure of turbidity and surface low‐turbidity stripes form inside the plume. Multiple fronts also have significant effects on the accumulation of surface materials.

Bioinspired Moisture‐Driven Soft Robotic Actuator

Multifunctional materials in nature, utilizing atmospheric water content, offer solutions to challenges in soft‐actuating materials research. The leaf of Arundo donax, an invasive plant, showcases exceptional properties: structural integrity, passive actuation, tunability, load‐bearing capacity, longevity, and an integrated battery‐free fluid generation and distribution mechanism. These functions coexist within a thin (≈130 μm) and lightweight structure with simple compositions. The study investigates material composition, passive fluid transport, water harvesting structures, and mechanical properties, revealing unexpected correlations between surface and internal structures. Additionally, tunable actuation, suitable for origami‐based mechanisms, is explored. Testing an energy‐free, moisture‐triggered soft robotic gripper, its ability to lift over 50 times its weight while maintaining sufficient softness for delicate tasks is demonstrated. This unit‐wise structure‐based actuation offers promise for soft robotics, with favorable fabrication possibilities and motion manipulation.

Tuning the surface structure of zinc oxide nanorods by oxide entities of Ni for enhanced degradation of chlorophenoxy herbicide and chlorinated phenols

The surface of hexagonal ZnO was subjected to preliminary treatment with Ni2+ ions that transformed into a homogeneously coated layer by air calcination process in the loading range of 0.3–5 % with respect to the weight of ZnO support. The enhanced absorption in the visible region evidenced the formation of a visible light-responsive oxide entities of Ni2+ and Ni3+ that was further authenticated by multiple edges of variable energy in bandgap analysis. The photoluminescence (PL) spectra revealed the potential role of surface oxides in prolonging the life span of photon-induced excitons. The majority formation of Ni2O3 among the oxide entities, as the surface layer was substantiated by XRD and XPS analysis. The homogeneity, texture, and microstructure of the coated layer were examined by FESEM and HRTEM analysis. The charge retention ability as a function of the thickness of the coated layer was estimated by chronopotentiometry whereas the SPIES measurements coupled with Mott-Schottky analysis facilitated the fetching of the flat band potential as well as the semiconducting electrical nature of the coated materials. The loading of the catalysts as well as the impregnation level for optimum degradation/removal was evaluated in sunlight exposure for the removal of 4-chlorophenol (4-CP). The catalyst with optimum activity i.e. 0.5 % Ni2+ impregnated ZnO, was tested for the removal of potential carcinogens that included 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,4-dichlorophenoxyacetic acid (2,4-D). The progress of the removal process was monitored by HPLC, and the extracted data was used for kinetic studies. The efficacy of the synthesized catalysts was further evaluated for the removal of a concoction of chlorophenol isomers i.e., 2-chlorophenol (2-CP), 3-chlorophenol (3-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,5-dichlorophenol (2,5-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP), both in complete spectrum and visible region (400–800 nm) natural sunlight exposure and established the kinetics of the degradation process.

Surface‐Engineered Pt‐Ni(111) Nanocatalysts for Boosting Their ORR Performance via Thermal Treatment

AbstractThe electrochemical oxygen reduction reaction (ORR) is critical for fuel cell application, and modifying surface structures of electrocatalysts has proven effective in improving their catalytic performances. In this study, we investigated surface‐engineered Pt−Ni nano‐octahedra subjected to annealing in various atmospheres. All octahedral nanocrystals retained their Pt−Ni {111} facets at an elevated temperature following the annealing treatments. Air annealing led to the formation of nickel‐rich shells on the Pt−Ni surface. In contrast, hydrogen (H₂) as a reducing gas facilitated the reduction of surface Ni species, incorporating them into the Pt−Ni bulk alloy, which resulted in superior mass activity and specific activity for ORR‐approximately 2.4 and 2.3 times as high as those from the unmodified counterpart, respectively. After 20,000 potential cycles, the H₂/Ar‐annealed Pt−Ni nano‐octahedra maintained a mass activity of 3.92 A/ , surpassing the initial mass activity of the unannealed counterparts (2.95 A/ ). These findings demonstrate a viable approach for tailoring catalyst surfaces to enhance performance in various energy storage and conversion applications.

Optimization of MBE-grown GaSb buffer on GaAs substrates for infrared detectors

The aim of this work was to improve the quality of the GaSb buffer layers on GaAs substrates using the molecular beam epitaxy (MBE) technology. The high quality of the GaSb buffer layers is one of the most important elements enabling the synthesis of good quality of type II superlattices (T2SL) structures for infrared applications. The main challenges in this regard are: compensation of the difference in lattice constants between GaAs and GaSb and obtaining the highest achievable surface quality of the final GaSb layer. In the literature, many authors describe different techniques to obtain the best quality of a GaSb buffer layer. In this work, we present the results of HRXRD, AFM, TOF-SIMS, SEM, and Nomarski optical microscope measurements obtained for 2 μm thick GaSb buffer layers. The GaSb layers are made according to different techniques and these results are compared with a GaSb buffer construction technique according to our own technology. During the processes, we also obtained an unintentional structure of one of the buffer layers, which allowed us to obtain very good results in terms of surface structure and crystallographic quality where FWHM in ωRC scan was equal to 138 arcsec and RMS 0.20 nm proving that there is still a lot of work to be done in this area.

Organic-Inorganic Biocompatible Coatings for Temporary and Permanent Metal Implants.

The general trend of increasing life expectancy will consistently drive the demand for orthopedic prostheses. In addition to the elderly, the younger population is also in urgent need of orthopedic devices, as bone fractures are a relatively common injury type; it is important to treat the patient quickly, painlessly, and eliminate further health complications. In the field of traumatology and orthopedics, metals and their alloys are currently the most commonly used materials. In this context, numerous scientists are engaged in the search for new implant materials and coatings. Among the various coating techniques, plasma electrolytic oxidation (PEO) (or micro-arc oxidation-MAO) occupy a distinct position. This method offers a cost-effective and environmentally friendly approach to modification of metal surfaces. PEO can effectively form porous, corrosion-resistant, and bioactive coatings on light alloys. The porous oxide surface structure welcomes organic molecules that can significantly enhance the corrosion resistance of the implant and improve the biological response of the body. The review considers the most crucial aspects of new combined PEO-organic coatings on metal implants, in terms of their potential for implantation, corrosion resistance, and biological activity in vitro and in vivo.

Biomimetic 3D-Printed Armored Structures for Durable Superhydrophobic Surfaces: Integrating Macroprotection and Nanofunctionality

Biomimetic 3D-Printed Armored Structures for Durable Superhydrophobic Surfaces: Integrating Macroprotection and Nanofunctionality

Anion Chemistry towards On‐Site Construction of Solid‐Electrolyte Interface for Highly Stable Metallic Zn Anode

AbstractReversibility of metallic Zn anode serves as the corner stone for the development of aqueous Zn metal battery, which motivates scrutinizing the electrolyte‐Zn interface. As the representative organic zinc salt, zinc trifluorosulfonate (Zn(OTf)2) facilitates a broad class of aqueous electrolytes, however, the stability issue of Zn anode remains crucial. The great challenge lies in the lack of Zn anode protection by the pristinely formed surface structure in aqueous Zn(OTf)2 electrolytes. Accordingly, an electrochemical route was developed to grow a uniform zinc trifluorosulfonate hydroxide (ZTH) layer on Zn anode as an artificial SEI, via regulation on metal dissolution and strong coordination ability of zinc ions. Co‐precipitation was proposed to be the formation mechanism for the artificial SEI, where the reduction stability of OTf− anion and the low‐symmetry layer structure of ZTH was unmasked. This artificial SEI favors interfacial kinetics, depresses side reactions, and well maintains its integrity during cycling, leading to a prolonged lifespan of Zn stripping/plating with a high DOD of ~85 %, and an improved cycling stability of ~92 % retention rate for V2O5/Zn cell at 1 A g−1. The unveiled role of anion on Zn anode drives the contemplation on the surface chemistry for the blooming aqueous rechargeable battery.

Ultraviolet laser induced periodic surface structures positively influence osteogenic activity on titanium alloys.

Endoprostheses might fail due to complications such as implant loosening or periprosthetic infections. The surface topography of implant materials is known to influence osseointegration and attachment of pathogenic bacteria. Laser-Induced Periodic Surface Structures (LIPSS) can improve the surface topography of orthopedic implant materials. In this preclinical in vitro study, laser pulses with a wavelength in the ultraviolet (UV) spectrum were applied for the generation of LIPSS to positively influence formation of extracellular matrix by primary human Osteoblasts (hOBs) and to reduce microbial biofilm formation in vitro. Laser machining was employed for generating UV-LIPSS on sample disks made of Ti6Al4V and Ti6Al7Nb alloys. Sample disks with polished surfaces were used as controls. Scanning electron microscopy was used for visualization of surface topography and adherent cells. Metal ion release and cellular metal levels were investigated by inductively coupled plasma mass spectrometry. Cell culture of hOBs on sample disks with and without UV-LIPSS surface treatments was performed. Cells were investigated for their viability, proliferation, osteogenic function and cytokine release. Biofilm formation was facilitated by seeding Staphylococcus aureus on sample disks and quantified by wheat germ agglutinin (WGA) staining. UV-LIPSS modification results in topographies with a periodicity of 223nm ≤ λ ≤ 278nm. The release of metal ions was found increased for UV-LIPSS on Ti6Al4V and decreased for UV-LIPSS on Ti6Al7Nb, while cellular metal levels remain unaffected. Cellular adherence was decreased for hOBs on UV-LIPSS Ti6Al4V when compared to controls while proliferation rate was unaffected. Metabolic activity was lower on UV-LIPSS Ti6Al7Nb when compared to the control. Alkaline phosphatase activity was upregulated for hOBs grown on UV-LIPSS on both alloys. Less pro-inflammatory cytokines were released for cells grown on UV-LIPSS Ti6Al7Nb when compared to polished surfaces. WGA signals were significantly lower on UV-LIPSS Ti6Al7Nb indicating reduced formation of a S. aureus biofilm. Our results suggest that UV-LIPSS texturing of Ti6Al7Nb positively influence bone forming function and cytokine secretion profile of hOBs in vitro. In addition, our results indicate diminished biofilm formation on UV-LIPSS treated Ti6Al7Nb surfaces. These effects might prove beneficial in the context of long-term arthroplasty outcomes.

Anion Chemistry towards On-Site Construction of Solid-Electrolyte Interface for Highly Stable Metallic Zn Anode.

Reversibility of metallic Zn anode serves as the corner stone for the development of aqueous Zn metal battery, which motivates scrutinizing the electrolyte-Zn interface. As the representative organic zinc salt, zinc trifluorosulfonate (Zn(OTf)2) facilitates a broad class of aqueous electrolytes, however, the stability issue of Zn anode remains crucial. The great challenge lies in the lack of Zn anode protection by the pristinely formed surface structure in aqueous Zn(OTf)2 electrolytes. Accordingly, an electrochemical route was developed to grow a uniform zinc trifluorosulfonate hydroxide (ZTH) layer on Zn anode as an artificial SEI, via regulation on metal dissolution and strong coordination ability of zinc ions. Co-precipitation was proposed to be the formation mechanism for the artificial SEI, where the reduction stability of OTf- anion and the low-symmetry layer structure of ZTH was unmasked. This artificial SEI favors interfacial kinetics, depresses side reactions, and well maintains its integrity during cycling, leading to a prolonged lifespan of Zn stripping/plating with a high DOD of ~85 %, and an improved cycling stability of ~92 % retention rate for V2O5/Zn cell at 1 A g-1. The unveiled role of anion on Zn anode drives the contemplation on the surface chemistry for the blooming aqueous rechargeable battery.

Hierarchical Micro/Nanostructures with Anti-Reflection and Superhydrophobicity on the Silicon Surface Fabricated by Femtosecond Laser.

In this paper, hierarchical micro/nano structures composed of periodic microstructures, laser-induced periodic surface structures (LIPSS), and nanoparticles were fabricated by femtosecond laser processing (LP). A layer of hydrophobic species was formed on the micro/nano structures through perfluorosilane modification (PM). The reflectivity and hydrophobicity's influence mechanisms of structural height, duty cycle, and size are experimentally elucidated. The average reflectivity of the silicon surface in the visible light band is reduced to 3.0% under the optimal parameters, and the surface exhibits a large contact angle of 172.3 ± 0.8° and a low sliding angle of 4.2 ± 1.4°. Finally, the durability of the anti-reflection and superhydrophobicity is also confirmed. This study deepens our understanding of the principles of anti-reflection and superhydrophobicity and expands the design and preparation methods for self-cleaning and anti-reflective surfaces.

Influence of Process Parameters on Flatness During Single-Track Laser Cladding.

During the laser cladding process, poor flatness of the cladding track can cause the surface structure to be uneven or corrugated, affecting the geometrical accuracy of the workpiece. Adjusting process parameters is an effective way to achieve high cladding track flatness. This study established a mesoscale model of the laser cladding process for CoCrMoSi powder to simulate the formation of a single cladding track. Subsequently, the formation mechanism of cladding track flatness was revealed by analyzing the flow within the molten pool and the solidification behavior of the molten pool edge. The influences of laser power, scanning speed, and powder feeding rate on flatness were determined through simulations and physical experiments. Finally, a parameter window of flatness was established using simulation and experimental results. The window indicates that high flatness is achieved with a high scanning speed (v > 260 mm/min), high laser power (P > 2300 W), and low powder feed rate (Pf < 5.5 g/min). The accuracy of the numerical model was verified by comparing the simulated results with the experimental measurements.

Improving the charging performance of latent heat thermal energy storage systems using triply periodic minimal surface (TPMS) structures

The utilization of latent heat thermal energy storage (LHTES) using phase change materials (PCM) has attracted considerable attention due to their high energy density and thermal regulation. However, the inferior thermal conductivity of PCM has hindered their widespread implementation, triply periodic minimal surface (TPMS) structures could considerably ameliorate the energy storage utilization. TPMS structures offer escalated surface area and pore interconnectivity, which can enhance the apparent thermal conductivity and improve the performance of LHTES systems. This study focuses on investigating the performance and storage capabilities of three unique TPMS structures, namely Gyroid, IWP, and Primitive, at different relative densities and charging temperatures. The computational model is developed, verified, and validated with the relevant experiment results. A comparative analysis of the temperature distribution and liquid fraction evolution in TPMS LHTES units is carried out and compared to pure PCM LHTES. At a charging temperature of 80 °C, compared to the complete melting time of 7206 s for the pure PCM LHTES, the results demonstrate that the G10, IWP10, and P10-PCM LHTES achieve complete melting at 344 s, 276 s, and 368 s, respectively. This affirms the superiority of IWP structures in improving the melting rates due to their escalated surface areas and tortuous paths. The use of TPMS structures improves the total heat storage, heat storage rate, and volumetric heat storage density, while reducing the gravimetric heat storage density, compared to the pure PCM LHTES. The G10-PCM LHTES attains total heat storage, heat storage rate, volumetric, and gravimetric heat storage density of 2120 J, 6.16 W, 63.6 kWh/m3, and 227 kJ/kg, compared to 1910 J, 0.27 W, 57.3 kWh/m3, and 250 kJ/kg for pure PCM LHTES, respectively. Moreover, increasing the relative density of TPMS structures adversely reduces the total heat storage, heat storage rate, and volumetric heat storage density, and significantly increases the heat storage rates. As the charging temperature increases, the complete melting time is reduced and the charging performance indicators are improved, for the pure PCM and TPMS-PCM LHTES units.

Neural correlates of masked priming: only morphologically derived words facilitate lexical decisions

ABSTRACT The visual processing of morphologically complex words has been studied for decades now. One influential account proposes initial sublexical parsing, based on surface structure, before semantic information comes in (form-first models; Rastle & Davis, 2008, Morphological decomposition based on the analysis of orthography. Language and Cognitive Processes, 23(7-8), 942–971. https://doi.org/10.1080/01690960802069730). We tested this account in German, a morphologically rich language in a masked-priming lexical decision study with (pseudo-)derived German words. Behavioural data showed masked priming for truly morphologically complex (e.g. farmer – FARM), but not for pseudo-complex (e.g. corner – CORN) or merely form-related primes (e.g. cartel – CAR). MEG data revealed an early sensitivity to form (140–330 ms), followed by a differentiation between derived and other primes (260–480 ms), challenging the notion of early blind decomposition. The results align with the AUSTRAL model (Taft, 2023, Localist lexical representation of polymorphemic words. In D. Crepaldi (Ed.), Linguistic morphology in the mind and brain (1st ed., pp. 152–166). Routledge. https://doi.org/10.4324/9781003159759-11) and suggest that German speakers have heightened sensitivity to morpho-semantic information, unlike English speakers, which likely due to differences in morphological complexity between languages.

Defect Chemistry of Titanium Dioxide (Rutile). Progress Toward Sustainable Energy.

This work, which overviews defect chemistry of TiO2 (rutile), is focused on atomic-size structural defects that are thermodynamically reversible. Here it is shown that thermodynamics can be used in defect engineering of TiO2-based energy materials, such as photoelectrodes and photocatalysts. We show that surface segregation of defects leads to the building-up of new surface structures that are responsible for reactivity. Since rational design of surface properties requires in situ surface characterization in operational conditions, expansion of bulk defect chemistry to surface defect chemistry requires a defect-related surface-sensitive tool for in situ monitoring of defect-related properties at elevated temperatures corresponding to defect equilibria and in a controlled gas-phase environment. Here we show that the high-temperature electron probe is a defect-related surface-sensitive tool that is uniquely positioned to aid surface defect engineering and determine unequivocal surface properties. The related applied aspects are considered for photoelectrochemical water splitting and the performance of solid oxide fuel cells. Here we report that trail-blazing studies on in situ surface monitoring of TiO2 during gas/solid equilibration, along with in situ characterization of surface semiconducting properties, leads to the discovery of a segregation-induced low-dimensional surface structure that is responsible for stable performance of oxide semiconductors, such as TiO2, in operational conditions.

Wideband and wide-angle microwave absorber via an integrated frequency selective surface and lattice structure design

Wideband and wide-angle microwave absorber via an integrated frequency selective surface and lattice structure design