Formation Of Layer Research Articles

Optimization of surface filtration to enhance wafer uniformity by removing large particle in ceria slurry

Owing to the limitations of scaling down, the development of complex structures for chip design is progressing in the semiconductor industry. As a result, the chemical mechanical polishing (CMP) process has become essential for the precise control of micro-level steps and for maintaining surface uniformity between layers during the stacking process. Structural management and improved performance of the consumables used in CMP processes are required. In particular, controlling the abrasive particles in the slurry that directly contact the wafer surface is crucial. Large particles within the slurry can occur scratches and cause non-uniformity in the polishing process, thus the particle size distribution of the slurry must be regulated. In this study, two types of filtration systems were constructed to determine the optimal conditions for CMP of ceria slurry. Depth filtration effectively removes particles through a cake layer formation mechanism but has limitations in achieving a consistent pore size within the fiber layer. Consequently, separation efficiency for particle sizes is relatively low. In contrast, surface filtration consisting of a single membrane demonstrates a consistent correlation between pore size and the size of the filtered particles, resulting in high particle removal efficiency. The pore size capable of removing large particles without active particle loss was 200 nm. After evaluating slurry productivity and filter-induced agglomeration, 0.8 L per minute (LPM) was identified as the optimal flow rate. Additionally, after filtration at 0.8 LPM, the maximum reduction in removal rates was relatively small at 272.54 Å/min due to decreased edge removal rates. However, by removing large particles to implement a monodisperse state, an improvement in uniformity of 17.11 % was achieved. Therefore, the CMP performance can be enhanced using surface filtration to control the particle size distribution (PSD).

Molecular simulation of the effect of water content on CO2, CH4, and N2 adsorption characteristics of coal

The objective of this work was to investigate the sorption behavior of gases, namely CO2, CH4, and N2, by molecules of coal sampled from Linglu mine under different water inclusion rates. To this end, the adsorption, diffusion, adsorption heat, and potential energy distribution characteristics of the gases in the coal pores at different water inclusion rates were analyzed using molecular dynamics and grand canonical ensemble Monte Carlo methods. The results showed that the adsorption relationship of the coal molecules on CO2, CH4, and N2 exhibited a downtrend followed by an uptrend when the water content was increased from 0 to 3.6%. The adsorption amount of CO2 was approximately twice as much as those of CH4 and N2, indicating that the competitive adsorption advantage of CO2 compared with those of CH4 and N2 was unaffected by the water content. The trend in the average heat of adsorption was generally consistent with the trend in the density of coal molecules under different moisture contents. Under the same conditions, the diffusion coefficient within a coal molecule was negatively related to the water content in the system. The layer spacing of the water molecules (2.875 Å) was greater than the liquid–water layer spacing, indicating the formation of a water molecule layer at this point, which inhibited gas adsorption. This study lays a theoretical foundation for further investigating the microscopic mechanism of coal–water interaction.

Insights from Li and Zn systems for advancing Mg and Ca metal batteries.

The inherent limitations of lithium (Li)-ion batteries have sparked interest in exploring alternative technologies, especially those relying on metallic anodes: monovalent Li and divalent zinc (Zn), magnesium (Mg), and calcium (Ca) metals. In particular, Mg and Ca metal batteries offer significant advantages based on the natural abundance of their raw materials and high energy-storage capabilities resulting from the bivalency of the carrier ions. Yet, these battery systems are far from commercialization, and the lack of reliable electrolytes constitutes a primary concern. The formation of ion-insulating passivation layers on these metallic anodes and their inferior desolvation kinetics have long been recognized as formidable hurdles in the way of optimizing the electrolyte composition. These impediments call for innovative strategies in electrolyte engineering and an extensive analysis of the resulting solid-electrolyte-interphase (SEI) layer. In this review, we introduce recent pioneering studies of divalent Mg and Ca metal batteries that have been concerned with these issues. This review particularly focuses on drawing an analogy with Li and Zn metal batteries in terms of the relative advancement and by benchmarking against the strategies developed for these analogous systems. The areas of interest include a fundamental understanding of the thermodynamics and evolution of the morphology of metallic anodes, a correlation between the electrolyte and SEI compositions, state-of-the-art electrolyte strategies to realize reversible (de)plating of Mg and Ca, and new perspectives on the SEI properties and their relevance to corrosion and the calendar life. We finally encourage researchers in the community to delve into these emerging areas by linking with successful stories in the analogous systems, but identifying distinct aspects of Mg and Ca batteries that still require attention.

Evaluating the bio-functionalities of Ti-6Al-7Nb alloy after surface modification using electrical discharge machining

Abstract The present work evaluates the influence of surface modification on the bio-functionalities of Ti-6Al-7Nb alloy in terms of apatite formation, metal ion release rate and anti-bacterial activities. The surface modification in the form of change in surface integrity, and increases in the exposed surface area, has been achieved using wire-electrical discharge machining (WEDM) and electrical dischargeµ-drilling(EDD). Due to high discharge energies, molten material will deposit on the parent material (recast layer), which increases the surface roughness (parent surface 0.5µm to 2.34µm) and hardness (patent material 304VH to 385VH) after subsequent re-solidification and quenching. Surface roughness and hardness near the micro-drilled hole are observed to increase. After surface modification, the apatite formation is increased on Ti-6Al-7Nb alloy with increasing immersion time and the ion released rate was found lowest on the WEDMed surface as compared to micro drilled and polished surface. Field-emission electron scanning microscopy (FESEM) and energy dispersive X-ray spectroscopy (EDAX) observations confirmed the presence of phosphate and calcium ions on the WEDMed surface and nearby the micro-drilled surface. The variation in colour of the simulated body fluid(SBF)after the immersion of WEDMed, EDD, and polished samples indicates the variable effect on pH levels of the SBF solution for three types of samples. The anti-bacterial bioactivity of Ti-6Al-7Nb was found to be better on the WEDMed surface as compared to polished surfaces, which is due to the formation of a rutile-TiO2 layer on WEDMed surface.

The Influence of Using Recycled Waste Aggregates and Adding TiO2 Nanoparticles on the Corrosion Resistance of Steel Reinforcement Embedded in Cementitious Composite

The aim of this paper was to examine the effects of adding TiO2 nanoparticles to cementitious compositions and partially substituting natural aggregates with recycled aggregates consisting of glass, brick, slag, or textolite, and to examine the material’s ability to resist corrosion under the action of chloride ions existent in the environment that attack the steel reinforcement. The results show that the changes in the cementitious composite when it comes to the composition and microstructure influence the formation of the oxide passivating layer of the reinforcement. The addition of TiO2 nanoparticles and recycled aggregates impacts the kinetics and corrosion mechanism of the reinforcement. An addition of 3% TiO2 was found to be optimal for reinforcement protection. Electrochemical impedance spectroscopy confirmed the results obtained by open-circuit potential and linear polarization tests. The classification of favorable conditions indicates that compositions with recycled aggregates and 3% TiO2 are the most effective, with compositions in which the natural aggregates were partially substituted with slag being the most effective.

Control of work functions of nanophotonic components

Work function is an essential material’s property playing important roles in electronics, photovoltaics, and more recently, in nanophotonics. We have studied effects of organic, and inorganic dielectric materials on work functions of Au films in single layered, and multilayered structures. We found that measured work function of metallic surfaces can be affected by dielectric materials situated 10–100 nm away from the metallic surface. We have found that, (i) the glass underneath ~ 50 nm gold slab reduces the work function of gold, (ii) Rh590:PMMA increases the work function of a gold film deposited on top of the polymer, and (iii) reduces it if Rh590:PMMA is deposited on top of Au. (iv) With increase of the Rh590 concentration in PMMA, n, the work function first decreases (at n < 64 g/l), and then increases (at n > 64 g/l). (v) The work function of a Fabry–Perot cavity or an MIM waveguide is almost the same as that of single Au films of comparable thickness. The experimental results can be qualitatively explained in terms of a simple model taking into account adhesion of charged molecules to a metallic surface, and formation of a double layer of charges accelerating or decelerating electrons exiting the metal and decreasing or increasing the work function.

Effect of surface hydroxyl group density of support membrane on water permeance of polyamide thin-film composite membrane

Polyamide-based thin-film composite (TFC) membranes are widely used in water treatment processes. Recently, the influence of support membranes on the performance of polyamide layers has garnered considerable attention. Regarding the chemical properties of the support membranes, the surface wettability and the interaction between the amine monomer used for interfacial polymerization and the membrane surface are considered to play crucial roles. In this study, we investigated the effect of the wettability of the support membrane surface and its interaction with the amine monomer on the water permeance of TFC membranes. We prepared TFC membranes on polyketone support membranes with varying surface hydroxyl group densities and aqueous solution wettabilities. While no clear correlation was observed between the support membrane’s wettability and the water permeance of the TFC membrane, an increase in hydroxyl group density did result in higher water permeance. The hydroxyl groups interact with PIP, inhibiting PIP diffusion and potentially leading to the formation of a thinner polyamide layer, which enhances water permeance. Therefore, the interaction between the amine monomer and support membrane surface strongly affects the formation of the polyamide layer.

Cellulose Nanofiber-Based Nanocomposite Films with Efficient Electromagnetic Interference Shielding and Fire-Resistant Performance.

Cellulose nanofiber (CNF) has been widely used as a flexible and lightweight polymer matrix for electromagnetic shielding and thermally conductive composite films because of its excellent mechanical strength, environmental performance, and low cost. However, the lack of flame retardancy seriously hinders its further application. Herein, renewable and biomass-sourced l-arginine (AR) was used to surface-modify ammonium polyphosphate (APP) and an environmentally friendly biobased flame retardant was synthesized by the coordination of zinc sulfate heptahydrate (ZnSO4·7H2O), which was named AAZ. AAZ was deposited on the surface of CNF by electrostatic adsorption and Zn2+ complexation. The biobased compatibilizer Triton X-100 was employed to assist the exfoliation of graphene nanoplatelets (GNPs) and their dispersion in the CNF matrix. Due to the formation of a dense lamellar layer resembling a shell structure, the CNF/GNPs composite films with a tensile strength of 52 MPa were obtained via vacuum-assisted filtration. Because the phosphorus-containing group produces a protective layer of PxOy compound and promotes the formation of a carbon layer by CNF and the combustion releases ammonia gas, the fire-resistant performance of the composite films was greatly improved. Compared with the pure CNF film, the composite film exhibits 33% reduction in PHRR value and 40% reduction in THR. In addition, the CNF/GNPs composite film with 20 wt % GNPs possessed high conductivity (2079.2 S/m) and electromagnetic interference (EMI) shielding effectiveness (37 dB). The ultrathin CNF/GNPs composite films have excellent potential for use as efficient flame retardant and EMI shielding materials.

Construction of biomass-based flame-retardant, antimicrobial and hydrophobic wood coatings with POSS organic–inorganic nanoparticles

The present study utilizes chitosan (CS) and phytic acid (PA) as natural polyelectrolytes, while incorporating Polyhedral Oligomeric Silsesquioxane (POSS), an organic–inorganic hybrid Si-O-Si cage structure, to create a flame retardant, antimicrobial, and hydrophobic coating for wood materials using the layer-by-layer self-assembly method. The POSS flame retardant bisDOPO-NH2-POSS was synthesized by combining 9,10-dihydro-9-oxa-10-phosphaphenathrene (DOPO) with octaminopropyl silsesquioxane (OA-POSS). Subsequently, AgNPs were incorporated into the cage structure of bisDOPO-NH2-POSS through in-situ reduction to fabricate Ag@bisDOPO-NH2-POSS for enhanced antimicrobial efficacy. The CS/PA coating was deposited using the LBL method, which resulted in the formation of a dense char layer during combustion due to both the presence of an inorganic Si-O-Si physical barrier and the synergistic effect of P-N-Si. As a result, self-extinguishing behavior was observed during vertical burning tests, and there was an increase in the limiting oxygen index value to 30.9%. Moreover, by incorporating chitosan, Ag@bisDOPO-NH2-POSS exhibited inhibitory effects against mold such as Aspergillus niger and Lasiodiplodia. The heat release rate (HRR) was reduced by 42.3%, while the total heat release (THR) decreased by 44.4%. The modified wood demonstrates exceptional water repellency, characterized by a static contact angle exceeding 90°. Additionally, the multifunctional coating shows remarkable resilience as it withstands 100 abrasion cycles without compromising its hydrophobic properties. This study presents a sustainable approach to developing a bio-based coating for wood materials that is flame retardant, hydrophobic, and antimicrobial, thereby expanding the potential applications of wood in construction and furniture.

A Model for Mechanical Stress Limited Bacterial Growth and Resporulation in Confinement.

In this study, we propose a self-limiting growth model forBacillus subtilisspores confined within porous polyacrylamide (PA) hydrogels. We observed thatB. subtilisspores germinate into vegetative cells within the hydrogel matrix, forming spherical colonies. These colonies expand until the mechanical stress they exert on their environment surpasses the yield stress of the hydrogel, leading to formation of a nonpermeable layer that halts nutrient diffusion and forces the bacteria to resporulate. These novel observations suggest a model to explain why bacterial growth in confined environments and material interfaces may be limited, providing insight for natural phenomena and biotechnological applications involving bacterial encapsulation.

Physicochemical Properties of (La,Sr)CoO3 Thick Films on Fe-25Cr Steel under Exposure to SOFC Cathode Operating Conditions

La0.6Sr0.4CoO3 (LSC) coatings with a thickness of 50–100 µm were deposited on Fe-25Cr ferritic stainless steel (DIN 50049) via screen printing. The required suspension had been prepared using fine LSC powders synthesised using EDTA gel processes. In its bulk form, the LSC consisted entirely of the rhombohedral phase with space group R-3c, and it exhibited high electrical conductivity (~144 S·cm−1). LSC-coated steel was oxidised in air at 1073 K, i.e., under conditions corresponding to SOFC cathode operation, for times of up to 144 h. The in situ electrical resistance of the steel/La0.6Sr0.4CoO3 layered system during oxidation was measured. The products formed on the samples after the oxidation reaction resulting from exposure to the corrosive medium were investigated using XRD, SEM-EDS, and TEM-SAD. The microstructural, nanostructural, phase, and chemical analysis of films was performed with a focus on the film/substrate interface. It was determined that the LSC coating interacts with the oxidised steel in the applied conditions, and a multi-layer interfacial zone is formed. Detailed TEM-SAD observations indicated the formation of a main layer consisting of SrCrO4, which was the reaction product of (La,Sr)CoO3, and the Cr2O3 scale formed on the metal surface. The formation of the SrCrO4 phase resulted in improved electrical conductivity of the investigated metal/ceramics layered composite material, as demonstrated by the low area-specific resistance values of 5 mΩ·cm2, thus making it potentially useful as a SOFC interconnect material operating at the tested temperature. In addition, the evaporation rate of chromium measured for the uncoated steel and the steel/La0.6Sr0.4CoO3 layered system likewise indicates that the coating is capable of acting as an effective barrier against the formation of volatile compounds of chromium.

Dynamic transition of internal oxides during high dew point heat treatment in Fe-2.4Mn-0.4Si-0.13 C alloy

The origin of the dynamic transition of internal oxides was clarified in Fe-2.4Mn-0.4Si-0.13C-based steel during decarburization annealing at 1073K. High dew point with H2 gas leads to the formation of deep decarburized ferrite layers containing grain boundary internal oxides. Microstructural characterization reveals the oxide transition from Mn2SiO4 to α-SiO2 at the tip of the internal oxidation layer and from α-SiO2 to Mn2SiO4 at the middle range of the internal oxidation layer. The dynamic transition between Mn2SiO4 and α-SiO2 is understood by the depletion in Mn contents and change of oxygen content, which change the normalized driving force of both oxides. The study gives a detailed mechanism of internal oxide formation and growth in multi-phase steel during high dew point annealing. Impact statementDuring high dew-point decarburization annealing, the fluctuation of Mn contents affects the driving force to form an internal oxide, resulting in the dynamic transition between Mn2SiO4 and α-SiO2.

Effect of thiol adsorption on the electrical resistance of copper ultrathin films

The impact of thiol adsorption on thin copper films, covered with a copper oxide layer, was investigated using electrical resistance measurements at various stages: during film growth, aging, exposure to air, and immersion in thiol solutions. Thin copper films (20 nm) were thermally evaporated, with variations in substrate temperature (RT, 330 and 390 K). Films deposited at 330 K exhibited the smallest percolation thickness and aging rates due to their compact morphology, showcasing lower surface roughness and correlation length. Exposure to air led to the formation of a Cu2O layer on the film surface. Subsequent immersion in a dodecanethiol solution in ethanol resulted in a resistance increase, ranging from 0.1 % to 0.4 %. This change was dependent on the substrate temperature, with the largest difference observed at 330 K. This observation suggests that samples grown at this temperature exhibited the highest electron-surface scattering. Moreover, by depositing a chromium surfactant layer, the impact of this scattering mechanism was amplified, leading to a resistance increase of up to 1.2 %. Mayadas-Shatzkes theory provided a good description of these resistance changes. The negatively charged S-head of the adsorbed thiols alters the electric field experienced by conduction electrons in the Cu2O/Cu interface, modifying the electron-surface scattering.

Influencing the surface quality of free-standing wurtzite gallium nitride in ultra-high vacuum: Stoichiometry control by ammonia and bromine adsorption

Gallium nitride (GaN), a wide bandgap semiconductor with absorption and emission in the ultraviolet/visible range, is proposed as an alternative to metallic surfaces for assembling organic molecular structures aiming at optoelectronic applications. However, the formation of a persistent surface oxide layer in air considerably limits the use of GaN for well-defined interfaces. In this work, we have investigated, characterized and processed n-type free-standing c-plane hexagonal wurtzite GaN crystals grown by hydride vapor phase epitaxy and ammonothermal growth methods. Surface cleaning and full removal of the oxide layer on GaN surfaces could be reproducibly achieved via sputtering and annealing cycles, as evidenced by X-ray photoelectron spectroscopy and low-energy electron diffraction. Scanning tunneling microscopy, however, indicated substantial roughening of the GaN surface and the formation of unwanted Ga-rich islands and clusters. Although ammonia (NH3) and bromine (Br) treatments compensated the N/Ga atoms ratio reduced by sputtering, the surface morphology remained rough, exhibiting randomly shaped and distributed hillocks. In addition, we studied the effect of electron bombardment on the surface quality of GaN during NH3 annealing, on-surface debromination and polymerization of 1,3,5-Tris(4-bromophenyl) benzene on GaN and removal of Ga atoms by Br atoms during the desorption.

New insights into aluminium anodizing in phosphonic acid

Aluminium anodizing in phosphonic acid is known to produce anodic aluminium oxide (AAO) honeycomb structures with large interpore distances. However, detailed information on two-stage anodizing in phosphonic acid and annealing conditions required for the crystallization of AAO cell walls have not been reported yet. Here, the kinetics of aluminium anodizing in 1 M phosphonic acid and the thermal behaviour of the resulting AAO have been studied in detail. The apparent activation energy of aluminium anodizing is 65 kJ mol–1 and the AAO growth rate reaches 15 µm h–1 before oxide burning. A universal approach for stable two-stage anodizing at high voltages allowing to prevent porous structure rearrangement in the upper part of AAO is proposed. It involves the preliminary formation of a dense barrier alumina layer by anodizing in a weak acid electrolyte before the second anodizing step in phosphonic acid. The crystallization pathways of AAO obtained in phosphonic acid electrolyte are revealed based on differential scanning calorimetry, X-ray diffraction, and solid-state nuclear magnetic resonance techniques. The designed annealing program allows one to preserve the honeycomb porous structure after the crystallization of AAO in corundum at 1310°C for 60 h. AAO obtained in phosphonic acid possesses high thermal stability and, thus, is promising as a support for gas sensors and fuel cells.

The effects of aluminate compounds on the free Ba generation and electron emission performance of dispenser cathode

Free barium (Ba) is critical to the formation of the active layer on the surface of dispenser cathode, which is contributed to the electron emission properties of the cathode. The Ba in the active layer of the dispenser cathode is generated by the chemical reaction between aluminate compounds and tungsten (W) under vacuum and high temperature. Nowadays, the effect of aluminate compounds on the generation of free Ba is not clear. In this work, aluminate impregnants called 411, 532 and 612 impregnants were prepared by coprecipitation method. The structure of the dominate compounds in 411, 532 and 612 impregnants were determined with density functional theory (DFT) calculation and Rietveld structure refinement. It was found that the dominate compounds of 411, 532 and 612 impregnants are Ba3.5Ca0.5Al2O7, Ba5CaAl4O12 and Ba3CaAl2O7, respectively. Then, the temperature dependence of the thermodynamic properties, such as Debye temperature, entropy, heat capacity and enthalpy, of the aluminate compounds were calculated. Based on the thermodynamic properties, the potential chemical reaction between aluminate compounds and W are energetically determined by deviation Gibbs energy. The effects of different aluminate compounds on the free Ba generation were evaluated with the equilibrium Ba(g) amounts that generated by the chemical reactions between aluminate compounds and W. It is shown that the equilibrium Ba(g) amounts generated by Ba3.5Ca0.5Al2O7 is higher than that by Ba5CaAl4O12 and Ba3CaAl2O7, implying the superiority of electron emission performance of Ba3.5Ca0.5Al2O7. The electron emission densities of the dispenser cathodes that impregnated with the 411, 612 and 532 impregnants are 5.06, 4.31 and 4.05 A/cm2, respectively. It is revealed that the Ba3.5Ca0.5Al2O7 has superiority in generating free Ba, which agreed well with thermodynamic simulation results.

A Mechanism for Ice Layer Formation in Glacial Firn

A Mechanism for Ice Layer Formation in Glacial Firn

The Role of Triboloading Conditions in Tribolayer Formation and Wear Resistance of PES-Based Composites Reinforced with Carbon Fibers

In this paper, the tribological characteristics of polyethersulfone-based composites reinforced with short carbon fibers (SCFs) at aspect ratios of 14–250 and contents of 10–30 wt.% are reported for linear metal–polymer and ceramic–polymer tribological contacts. The results showed that the wear resistance could be greatly improved through tribological layer formation. Loading PES with 30 wt.% SCFs (2 mm) provided a minimum WR value of 0.77 × 10−6 mm3/N m. The tribological layer thicknesses were estimated to be equal to 2–7 µm. Several conditions were proposed, which contributed to the formation of a tribological layer from debris, including the three-stage pattern of the changing kinetics of the time dependence of the friction coefficient. The kinetics had to sharply increase up to ~0.4–0.5 in the first (running-in) stage and gradually decrease down to ~0.1–0.2 in the second stage. Then, if these levels did not change, it could be argued that any tribological layer had formed, become fixed and fulfilled its functional role. The PES-based composites loaded with SCFs 2 mm long were characterized by possessing the minimum CoF levels, for which their three-stage changing pattern corresponded to one of the conditions for tribological layer formation. This work provides valuable insight for studying the process parameters of tribological layer formation for SCF-reinforced thermoplastic PES composites and revealing their impact on tribological properties.

The effect of silicon dioxide on the structural, thermal and transport properties of an organic ionic plastic crystal (n-C4H9)4NBF4

Composite solid electrolytes based on an organic ionic plastic crystal (n-C4H9)4NBF4 with highly dispersed SiO2 with specific surface area of Ss = 324±10 m2/g have been studied for the first time. By methods of X-ray diffraction and differential scanning calorimetry, it was found that the introduction of SiO2 leads to amorphization of the salt. An unusual size effect was observed in the composites: the temperature of the polymorphic transition of the salt shifted from 67 °C to 60 °C, while the melting point did not change. The 0.15(n-C4H9)4NBF4–0.85SiO2 composite was found to possess the highest electrical conductivity (σ = 2∙10–5 S/cm at 150 °C), which is 1.5 orders of magnitude higher than that of the initial salt. Modelling of the concentration dependences of the electrical conductivity of composites using the mixing equation showed that the reason for the increase in electrical conductivity is the formation of an amorphous layer of salt, the electrical conductivity of which is 3 orders of magnitude higher than that of the crystalline phase (n-C4H9)4NBF4. The obtained results can be used for the design of high-performance composites based on organic ionic plastic crystals for application in electrochemical devices.

Elastomeric Fire and Heat-Protective Materials Containing Functionally Active Microheterogeneous Systems

This research aims to explore how functionally active structures affect the physical, mechanical, thermal, and fire-resistant properties of elastomeric compositions using ethylene–propylene–diene rubber as a base. The inclusion of aluminosilicate microspheres, microfibers, and a phosphorus–boron–nitrogen–organic modifier in these structures creates a synergistic effect, enhancing the material’s heat-insulating properties by strengthening coke and carbonization processes. This results in a 12–19% increase in heating time for unheated sample surfaces and a 6–17% increase in residual coke compared to existing analogs. Microspheres help counteract the negative impact of microfibers on composition density and thermal conductivity, while the phosphorus–boron–containing modifier allows for controlling the formation of the coke layer.