Mechanical properties of UV‐curable carbon fiber‐reinforced polymer composite patch: Repair evaluation of damaged aluminum alloy

Epoxy resin composite patches reinforced by carbon fiber were prepared through ultraviolet (UV)–curing method, and the damaged aluminum alloy plates are rapidly repaired by means of adhesively bonding method. Mechanical properties of the composite patches and damaged aluminum alloy plates before and after repair were studied by experiment and numerical simulation. Results indicated that the tensile properties of carbon fiber/epoxy resin composite patches presented the tendency of first increase and then decrease with the increase of layer numbers of reinforced fiber. The composite patches with two layers fiber showed the best tensile properties, and the tensile strength and modulus reached 1.13 GPa and 27.79 GPa, respectively. However, the bending strength of composite patches decreased with the increase of layer numbers. Results of performance evaluation on the mechanical properties of damaged aluminum alloy plates repaired by the two layers carbon fiber/epoxy resin composite patches showed that the repair efficiency of tensile and bending properties of the repaired aluminum alloys reached more than 83% and 160%, respectively, compared with the undamaged aluminum alloys. Besides, results of numerical simulation showed that the stress intensity factor (SIF) of the crack tip on repaired aluminum alloy plates decreased significantly in comparison with the unrepaired aluminum alloy plates, which further revealing the reinforced mechanism of composite patches on the bending properties of repaired aluminum alloy plates.     

The sodium responsive tungsten bronze electrode: An electrode for sodium ion analysis of DNA solutions

The preparation and construction of tungsten bronze electrodes, responsive to sodium ions, are reported. The electrodes were made from tungsten bronze powder (Na_0.4WO₃), compressed into pellets with a resin binder and sealed in epoxy resin.The electrodes were found to respond almost instantenously to changes in sodium ion concentration and to be relatively stable with time. The pH dependence decreases as the sodium ion concentration increases, indicating suitability for solutions of sea water concentration.Unfortunately the electrodes show a response to potassium ions of apparently equal magnitude to the sodium response between 0.001 mol kg⁻¹ and 0.1 mol kg⁻¹. Preliminary tests indicate that they also respond to lithium, calcium, aluminium, cupric and tetramethylammonium ions at concentrations of 0.1 mol kg⁻¹. At high sodium ion concentrations ( 1 mol kg⁻¹) the effect of cross sensitivity is negligible for these ions. No attempts are made in this short paper to evaluate selectivity coefficients. Some data demonstrating the low but linear response to sodium ion are given. Tests carried out in DNA—saline-bearing solutions suggest that the possible suitability for marine or biological applications.     

Grafting of hyperbranched poly(amidoamine) onto waste tire rubber powder and its potential application as the curing agent for epoxy resin

To realize the high‐valued application of waste tire rubber (WTR), hyperbranched poly(amidoamine) (PAMAM) were synthesized from the surface of WTR powders to endow its chemical reactivity. The hyperbranched PAMAM‐grafted WTR powders containing a large amount of amine groups on their surface were obtained through “divergent procedure.” First, methyl methacrylate‐grafted WTR powders (MMA‐g‐WTR) were prepared by ozone‐induced grafting polymerization. Afterwards, Michael reaction and subsequent amidation reactions were carried out repetitively to obtain hyperbranched PAMAM chains grafted from the surface of the MMA‐g‐WTR powders. The resulting hyperbranched PAMAM‐grafted WTR powders exhibit good dispersibility in water. Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis demonstrate the successful grafting of hyperbranched PAMAM on WTR surface. The hyperbranched PAMAM‐grafted WTR powder could be utilize as curing agent and potential toughener for epoxy resin due to abundant amine groups and elastomeric feature of WTR. Differential scanning calorimetry shows that the hyperbranched PAMAM‐grafted WTR powders can be used as effective curing agent for epoxy resin. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface Studies on Glass Powders Used in Commercial Glass-Ionomer Dental Cements

The surface properties of three commercial ionomer glass powders, i.e., Fuji IX, Kavitan Plus and Chemadent G-J-W were studied. Samples were analyzed by X-ray fluorescence spectroscopy (XRF), and the density was determined by gas pycnometry. Morphology was studied using scanning electron microscopy (SEM) and laser diffraction (LD) technique, whereas low-temperature nitrogen sorption measurements determined textural parameters like specific surface area and pore volume. Thermal transformations in the materials studied were evaluated by thermogravimetric analysis (TGA), which was carried out in an inert atmosphere between 30 °C and 900 °C. XRF showed that Fuji IX and Kavitan Plus powders were strontium-based, whereas Chemadent G-J-W powder was calcium-based. Powders all had a wide range of particle sizes under SEM and LD measurements. Specific surface areas and pore volumes were in the range 1.42–2.73 m²/g and 0.0029 to 0.0083 cm³/g, respectively, whereas densities were in the range 2.6428–2.8362 g/cm³. Thermogravimetric analysis showed that the glass powders lost mass in a series of steps, with Fuji IX powder showing the highest number, some of which are attributed to the dehydration and decomposition of the polyacrylic acid present in this powder. Mass losses were more straightforward for the other two glasses. All three powders showed distinct losses at around 780 °C and 835 °C, suggesting that similar dehydration steps occur in all these glasses. Other steps, which differed between glass powders, are attributed to variations in states of water-binding on their surfaces.     

Iron(III) Oxide Graphite Composite Electrodes: Application to the Electroanalytical Detection of Hydrazine and Hydrogen Peroxide

Composite electrodes based on iron(III) oxide, Fe₂O₃, carbon powder and epoxy resin have been prepared and characterized using electrochemical methods and X‐ray photoelectron spectroscopy (XPS). Initially composite electrodes were made by mixing micron sized carbon powder surface with iron(III) oxide. However, the voltammetric responses were unsatisfactory. Therefore, a new type of composite electrodes was made using carbon powder modified with iron(III) oxide via a wet impregnation procedure. This technique involves saturation of the carbon powder with iron(III) nitrate followed by thermal treatment at ca. 623 K forming iron(III) oxide on the surface of the carbon powder.     

Damage assessment of nanofiller-reinforced woven kevlar KM2plus/Epoxy resin laminated composites

The resiliency of advanced laminated nanocomposite materials to mitigate impact load is an essential characteristic for material selection and product design. This paper investigates the effect of nanofillers and its effect on the damage resistance performance of a newly developed woven Kevlar fabric. Three types of nanofillers were investigated: (1) Silicon carbide (SiC), (2) aluminum oxide (Al₂O₃), and (3) multiwalled carbon nanotube (MWCNT). The nanofillers were dispersed using shear mixing and sonication into the epoxy to reinforce Kevlar fabric. Moreover, the effect of the nanofiller's concentration on the damage resistance performance was analyzed. All specimens had 10 layers of Kevlar fabric (KM2plus) stacked with a 0° angle. To evaluate the damage resistance performance a drop-weight impact test was conducted using a maximum drop height of 100 cm. X-ray diffraction was used to evaluate the level of material damage caused by the impact load. The addition of nanofillers enhanced the flexural properties of the composite and as well as its resiliency towards impact loads. In particular, the 0.5 wt% MWCNT laminated Kevlar/epoxy composite possessed the highest impact damage resistance capacity. Furthermore, the damage evolution was not observed within the impact area and in the surrounding areas for specimens with 0.5 wt% MWCNT. Therefore, the results indicate that the optimal nanofiller content for Kevlar KM2plus/epoxy nanocomposites is 0.5 wt% MWCNTs.     

Characterization of Betabel Extract (Beta vulgaris) Encapsulated with Maltodextrin and Inulin

Betalains are powerful antioxidants contained in beets. These are divided into betacyanins (red-violet) and betaxanthins (yellow-orange), and they can be used as natural colorants in the food industry. The effects of freeze-drying pure beet juice (B) and the encapsulation of beet juice with a dextrose equivalent (DE) 10 maltodextrin (M) and agave inulin (I) as carrier agents were evaluated. The powders showed significant differences (p < 0.05) in all the variables analyzed: water absorption index (WAI), water solubility index (WSI), glass transition temperature (T_g), total betalains (TB), betacyanins (BC), betaxanthins (BX), total polyphenols (TP), antioxidant activity (AA, via 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) (ABTS), and 2,2-diphenyl-1-picrylhydrazyl (DPPH)) and total protein concentration (TPC). The highest values of antioxidant activity were found in the non-encapsulated beet powder, followed by the powder encapsulated with maltodextrin and, to a lesser extent, the powder encapsulated with inulin. The glass transition temperature was 61.63 °C for M and 27.59 °C for I. However, for B it was less than 18.34 °C, which makes handling difficult. Encapsulation of beet extract with maltodextrin and inulin by lyophilization turned out to be an efficient method to increase solubility and diminish hygroscopicity.     

Curing Kinetics Modeling of Epoxy Modified by Fully Vulcanized Elastomer Nanoparticles Using Rheometry Method

In this study, the curing kinetics of epoxy nanocomposites containing ultra-fine full-vulcanized acrylonitrile butadiene rubber nanoparticles (UFNBRP) at different concentrations of 0, 0.5, 1 and 1.5 wt.% was investigated. In addition, the effect of curing temperatures was studied based on the rheological method under isothermal conditions. The epoxy resin/UFNBRP nanocomposites were characterized via Fourier transform infrared spectroscopy (FTIR). FTIR analysis exhibited the successful preparation of epoxy resin/UFNBRP, due to the existence of the UFNBRP characteristic peaks in the final product spectrum. The morphological structure of the epoxy resin/UFNBRP nanocomposites was investigated by both field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) studies. The FESEM and TEM studies showed UFNBRP had a spherical structure and was well dispersed in epoxy resin. The chemorheological analysis showed that due to the interactions between UFNBRP and epoxy resin, by increasing UFNBRP concentration at a constant temperature (65, 70 and 75 °C), the curing rate decreases at the gel point. Furthermore, both the curing kinetics modeling and chemorheological analysis demonstrated that the incorporation of 0.5% UFNBRP in epoxy resin matrix reduces the activation energy. The curing kinetic of epoxy resin/UFNBRP nanocomposite was best fitted with the Sestak–Berggren autocatalytic model.     

Drop-weight impact tests and finite element modeling of cast acrylic/aluminum plates

As an extension of a previous study [1], drop-weight impact tests on cast acrylic (PMMA) plates reinforced by aluminum face sheets were carried out using an instrumented drop weight impact tester. The PMMA and aluminum layers were adhered by epoxy cured at room temperature. Depending on the impact velocity and the type of top surface (acrylic or aluminum) struck by the impactor, damage caused by impact included partial or full delamination at the interface and radial cracks in the acrylic layer. The higher the impact velocity, the more damage was induced. More severe damage occurred if the bi-layer plate was impacted on the aluminum side. The ultrasonic C-scan technique was adopted to detect the damage. The pulse-echo technique with a focused transducer provided very good C-scan results for detecting damage patterns. The transducer with higher frequency gave better resolution and showed more details of damage. Finally, the finite element program, LS-DYNA, implemented with maximum strength criterion for radial cracking and mixed mode strength criterion for interfacial fracture, was used to simulate the drop weight impact tests. Impact force history, energy partition and delamination were predicted assuming various boundary conditions according to experimental results. The finite element simulations were in very good agreement with the experimental data.     

Approach to improving the toughness of TGMDA/DDS epoxy resin by blending with thermoplastic polymer powders

A series of hot-melt processable thermosetting compositions was prepared by blending N,N,N′,N′-tetraglycidyl-4,4′ -diaminodiphenyl-methane/4,4′-diaminodiphenylsulfone (TGMDA/DDS) epoxy resin and thermoplastic polymer powders with average particle size below 30 μm. The basic thermoplastic polymers were either a high T_g amorphous cardo polyimide (T_g=350°C) or commercial semicrystalline PA6 and PA12 polyamides. The resulting heterogeneous mixtures showed viscosity values below 5000 cps suitable for prepregging process. After cure, phase-separated morphologies were maintained with a rather limited interphase miscibility as demonstrated by thermomechanical analysis. Scanning electron microscope examination of fracture surfaces pointed out a strong adhesion between the powder particles and the surrounding polyepoxy network, particularly for the potentially reactive polyamide structures. Moreover, as shown by differential scanning calorimeter analysis, the crystallinity ratio of the PA6 and PA12 powders was lowered due to melting during thermal polymerization. The fracture toughness properties of the powder-containing materials were compared with those of a fully miscible cardo polyimide–TGMDA/DDS blend coming from an homogeneous resin composition. The best improvement in fracture energy was obtained for the powder-modified resins. The most effective composition filled with 16 wt% of powdered polyimide exhibited a fourfold increase in G_IC (388 J/m² versus 100 J/m²) without compromising the epoxy thermomechanical stability (T_g=227°C versus 223°C).     

Electrophoretic Deposition of Hydroxyapatite Coatings on Metal Substrates: A Nanoparticulate Dual-Coating Approach

Hydroxyapatite coatings can be readily deposited on metal substrates by electrophoretic deposition. However, subsequent sintering is highly problematic owing to the fact that temperatures in excess of 1100°C are required for commercial hydroxyapatite powders to achieve high density. Such temperatures damage the metal and induce metal-catalysed decomposition of the hydroxyapatite. Furthermore, the firing shrinkage of the hydroxyapatite coating on a constraining metal substrate leads to severe cracking. The present study has overcome these problems using a novel approach: the use of aged nanoparticulate hydroxyapatite sols (lower sintering temperature) and a dual coating strategy that overcomes the cracking problem. Dual layers of uncalcined hydroxyapatite (HAp) powder were electrophoretically coated on Ti, Ti6Al4V and 316L stainless steel metal substrates, sintered at 875–1000°C, and characterised by SEM and XRD, and interfacial shear strength measurement. Dual coatings on stainless steel had an average high bond strength (about 23 MPa), and dual coatings on titanium and titanium alloy had moderate strengths (about 14 and 11 MPa, respectively), in comparison with the measured shear strength of bone (35 MPa). SEM and XRD demonstrated that the second layer blended seamlessly with the first and filled the cracks in the first. The superior result on stainless steel is attributed to a more appropriate thermal expansion match with hydroxyapatite, the thinner oxide layer, or a combination of these factors.     

Laser-induced breakdown spectroscopy for quantitative spectrochemical analysis of geological materials: effects of the matrix and simultaneous determination

A microscopic laser-induced breakdown spectrometer was used to evaluate the analytical matrix effect commonly observed in the analysis of geological materials. Samples were analyzed in either the powder or pressed pellet forms. Calibration curves of a number of iron and aluminum compounds showed a linear relationship between the elemental concentration and peak intensity. A direct determination of elemental content can thus be made from extrapolation on these calibration curves. To investigate matrix effects, synthetic model samples were prepared from various iron and aluminum compounds spiked with SiO₂ and CaCO₃. The addition of these matrices had a pronounced analytical effect on those compounds prepared as pressed pellets. However, results indicated the absence of matrix effects when the samples were presented to the laser as loose powders on tape and results were compared to certified values, indicating the reliability of this approach for accurate analysis, provided the sample particle diameters are greater than ≈100 μm. Finally, the simultaneous analysis of two different elements was demonstrated using powders on tape.     

Preparation of Quaternary Amphiphilic Block Copolymer PMA-b-P (NVP/MAH/St) and Its Application in Surface Modification of Aluminum Nitride Powders

Poly(methyl acrylate)-b-poly(N-vinyl pyrrolidone/maleic anhydride/styrene) (PMA-b-P (NVP/MAH/St)) quaternary amphiphilic block copolymer prepared by reversible addition-fragmentation chain transfer (RAFT) was used to improve the anti-hydrolysis and dispersion properties of aluminum nitride (AIN) powders that were modified by copolymers. Its structure was characterized by Fourier transform infrared spectroscopy (FT-IR) and Hydrogen nuclear magnetic spectroscopy (¹H-NMR). The results demonstrate that the molecular weight distribution of the quaternary amphiphilic block copolymers is 1.35–1.60, which is characteristic of controlled molecular weight and narrow molecular weight distribution. Through charge transfer complexes, NVP/MAH/St produces a regular alternating arrangement structure. After being treated with micro-crosslinking, AlN powder modified by copolymer PMA-b-P(NVP/MAH/St) exhibits outstanding resistance to hydrolysis and can be stabilized in hot water at 50 °C for more than 14 h, and the agglomeration of powder particles was improved remarkably.     

Carbothermal synthesis of ultra-fine zirconium carbide powders using inorganic precursors via sol–gel method

Ultra-fine zirconium carbide (ZrC) powders have been synthesized by carbothermal reduction reactions using inorganic precursors zirconium oxychloride (ZrOCl₂ · 8H₂O) as sources of zirconium and phenolic resin as the carbon source. The reactions were substantially completed at relatively lower temperatures (∼1400 °C/1 h) and the synthesized powders had a small average crystallite size (<200 nm) and a large specific area (54 m²/g). The oxygen content of the powder synthesized at 1400 °C/1 h was less than 1.0 wt%. The thermodynamic change process in the ZrO₂–C system and the synthesis mechanism were studied.     

Production of doped ZnO powders for varistor applications using sol-gel techniques

The electrical behaviour of ZnO varistors is controlled by the characteristics of the ceramic microstructure which depends strongly on the properties of the initial powder. This paper describes a study of the effect of different chemical methods to synthesise doped ZnO powders. The ceramic powders were synthesised by the following routes: a) classical mixing of oxides (for comparison purposes), b) aqueous solution of inorganic salts and c) hydrolysis and polycondensation of metalorganic compounds in an organic solvent. The physicochemical characteristics of these powders were evaluated using a scanning electron microscope and thermoanalytical instrumentation. Standard spray drying technology was used to pelletise the powders to obtain an agglomerated powder suitable for uniaxial pressing. The discs were sintered in an electric furnace under air atmosphere using several temperature programmes. The ceramic microstructure was characterised using SEM and X-ray diffraction. The effects of powder processing route on sintering and microstructural development are discussed. Powders prepared by the metalorganic route exhibited somewhat lower sintering temperatures than conventional powders. However, the rate of sintering was slower for metalorganic and aqueous solution powders. These observations were related to powder morphology. The ZnO–Bi₂O₃–CoO system exhibited the best varistor characteristics as it was expected, whereas the binary systems supported much lower voltages at low currents than ternary systems.     

Optimization of Fermentation Process of Pomegranate Peel and Schisandra Chinensis and the Biological Activities of Fermentation Broth: Antioxidant Activity and Protective Effect Against H2O2-induced Oxidative Damage in HaCaT Cells

In this study, the lactobacillus fermentation process of pomegranate (Punica granatum L.) peel and Schisandra chinensis (Turcz.) Baill (PP&SC) was optimized by using the response surface method (RSM) coupled with a Box-Behnken design. The optimum fermentation condition with the maximal yield of ellagic acid (99.49 ± 0.47 mg/g) was as follows: 1:1 (w:w) ratio of pomegranate peel to Schisandra chinensis, 1% (v:v) of strains with a 1:1 (v:v) ratio of Lactobacillus Plantarum to Streptococcus Thermophilus, a 37 °C fermentation temperature, 33 h of fermentation time, 1:20 (g:mL) of a solid–liquid ratio and 3 g/100 mL of a glucose dosage. Under these conditions, the achieved fermentation broth (FB) showed stronger free radical scavenging abilities than the water extract (WE) against the ABTS⁺, DPPH, OH⁻ and O₂⁻ radicals. The cytotoxicity and the protective effect of FB on the intracellular ROS level in HaCaT cells were further detected by the Cell Counting Kit-8 (CCK-8) assay. The results showed that FB had no significant cytotoxicity toward HaCaT cells when its content was no more than 8 mg/mL. The FB with a concentration of 8 mg/mL had a good protective effect against oxidative damage, which can effectively reduce the ROS level to 125.94% ± 13.46% (p < 0.001) compared with 294.49% ± 11.54% of the control group in H₂O₂-damaged HaCaT cells. The outstanding antioxidant ability and protective effect against H₂O₂-induced oxidative damage in HaCaT cells promote the potential for the FB of PP&SC as a functional raw material of cosmetics.     

Thermal diffusivity measurement of ceramic materials used in spraying of TBC systems

The basic goal of this article was thermal diffusivity characterization of ceramic materials used in thermal barrier coating (TBC) systems for depositions of the insulation layer and characterization of the materials’ morphology and remanufacturing process. The base material was oxide 8YSZ (ZrO_2? ×?8Y₂O₃), which is usually dedicated to deposition of an insulating top layer in TBC systems. The data related to thermal properties such as thermal diffusivity and thermal conductivity are widely presented in the literature, but there is lack of information about the morphological form of investigated materials, and the presented results vary widely. Data on thermal properties based on the literature sources are inadequate for the real morphological form of materials used in the experiment (e.g., massive or single crystalline material vs. plasma-sprayed coatings), which consequently gives an unsatisfactory accuracy of the obtained numerical simulations by MES methods. This article presents the characterization of thermal diffusivity of the commercial 8YSZ ceramic material synthesized or remanufactured by different routes, which is investigated in the forms of pressed powder pellet (two commercial nano-sized powders with different morphologies), sintered pellets (one commercial powder, solid-state co-precipitated reacted powder of 8YSZ type), and a two-layered coating system of In625?+?NiCrAlY/8YSZ type. The range of analysis included morphological investigations of different types of powders in initial conditions and after remanufacturing (sintering, thermal spraying) as well as the thermal diffusivity analysis by the laser flash method. The obtained data were corrected by porosity factor and compared to each other. The best similarity for obtained thermal diffusivity data was found for commercial powers of HOSP^TM type after pressing and sintering processes and calculated (2-layered model) value of thermal diffusivity for two-layered system of In625/8YSZ TBS system. The results showed that there are significant differences in thermal diffusivity values for materials with different morphological forms.

     

Efficient Adsorption of Chromium Ions from Aqueous Solutions by Plant-Derived Silica

Nowadays, there is great interest in the use of plant waste to obtain materials for environmental protection. In this study, silica powders were prepared with a simple and low-cost procedure from biomass materials such as horsetail and common reed, as well as wheat and rye straws. The starting biomass materials were leached in a boiling HCl solution. After washing and drying, the samples were incinerated at 700 °C for 1 h in air. The organic components of the samples were burned leaving final white powders. These powders were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS), scanning electron microscopy (SEM), and low-temperature nitrogen sorption. The amorphous powders (biosilica) contained mainly SiO₂, as indicated by FTIR analysis. Horsetail-derived silica was chosen for testing the removal of dichromate ions from water solutions. This biosilica had a good ability to adsorb Cr(VI) ions, which increased after modification of the powder with the dodecylamine surfactant. It can be concluded that the applied procedure allowed obtaining high purity biosilica from plant waste with good efficiency. The produced biosilica was helpful in removing chromium ions and showed low cytotoxicity to human endothelial cells, suggesting that it can be safely used in environmental remediation.     

Layering Optimization of the SrFe0.9Ti0.1O3−δ–Ce0.8Sm0.2O1.9 Composite Cathode

Cathode thickness plays a major role in establishing an active area for an oxygen reduction reaction in energy converter devices, such as solid oxide fuel cells. In this work, we prepared SrFe_0.9Ti_0.1O_3−δ–Ce_0.8Sm_0.2O_1.9 composite cathodes with different layers (1×, 3×, 5×, 7×, and 9× layer). The microstructural and electrochemical performance of each cell was then explored through scanning electron microscopy and electrochemical impedance spectroscopy (EIS). EIS analysis showed that the area-specific resistance (ASR) decreased from 0.65 Ωcm² to 0.12 Ωcm² with the increase in the number of layers from a 1× to a 7×. However, the ASR started to slightly increase at the 9× layer to 2.95 Ωcm² due to a higher loss of electrode polarization resulting from insufficient gas diffusion and transport. Therefore, increasing the number of cathode layers could increase the performance of the cathode by enlarging the active area for the reaction up to the threshold point.     

A Solid Fe2O3 Based Carbon–Epoxy Electrode for Potentiometric Measurements of pH

A solid Fe₂O₃ based carbon-epoxy composite electrode was investigated for use as a potentiometric pH sensor. The electrode was constructed using a mixture of sulfated iron(III) oxide, carbon power, and epoxy resin, which was deposited directly onto a glass tube. The effect of composition (Fe₂O₃, carbon and epoxy resin) on the electrode response and its calibration curve (mV/pH) were investigated. The analytical behavior of the electrode in acid–base titrations was compared with that of a glass electrode. A linear response from pH 1.7 to 12.2 with a slope of –39.7 ± 0.6 mV/pH (at 25°C) was observed.