Properties Modification of Fiber Metal Laminates by Nanofillers

During past decades, increasing demand of modified Fiber Metal Laminates (FMLs) has stimulated a strong trend towards the development of these structures. FMLs contain several thin layers of metal bonded with composite materials. Characteristics of FMLs such as low specific mass, high bearing strength, impact resistance, corrosion resistance and high fatigue life are attractive. Nowadays, increasing development can be observed to promote the properties of polymer-based composites by nanofillers. By dispersing strong, nanofillers in polymer matrix, modified composites can be developed and tailored to individual applications. On the other hand, the synergic effects of nanoparticles such as graphene and carbon nanotube can significantly improve the mechanical, electrical and thermal properties of nanocomposites. In present paper, the modifying of FMLs by nanofillers and the dispersing of nanoparticles in the polymers matrix are discussed. The evaluations have revealed that this approach is acceptable. Finally, a prospect is presented. This paper will lead to further work on these modified FML species.

Removal of Nitrogen Compounds from Industrial Wastewater Using Sequencing Batch Reactor: The Effects of React Time

This study was performed to optimise the react time (RT) and study its effects on the removal rates of nitrogen compounds in a sequencing batch reactor (SBR) treating synthetic industrial wastewater. The results showed that increasing the RT from 4 h to 10, 16 and 22 h significantly improved the nitrogen compounds’ removal efficiency, it was increased from 69.5% to 95%, 75.7 to 97% and from 54.2 to 80.1% for NH3-N, NO3-N and NO2-N respectively. The results obtained from this study showed that the RT of 22 h was the optimum for nitrogen compounds removal efficiency.

Obtaining Composite Cotton Fabric by Cyclodextrin Grafting

Finishing is an important part of fabric processing with which a wide range of features are imparted to greige or colored fabrics for various end-uses. Especially, by the addition or impartation of nano-scaled particles to the fabric structure composite fabrics, a kind of composite materials can be acquired. Composite materials, generally shortened as composites or in other words composition materials, are engineered or naturally occurring materials made from two or more component materials with significantly different physical, mechanical or chemical characteristics remaining separate and distinctive at the macroscopic or microscopic scale within the end product structure. Therefore, the technique finishing which is one of the fundamental methods to be applied on fabrics for obtainment of composite fabrics with many functionalities was used in the current study with the same purpose. However, regardless of the finishing materials applied, the efficient life of finished product on offering desired feature is low, since the durability of finishes on the material is limited. Any increase in durability of these finishes on textiles would enhance the life of use for textiles, which will result in happier users. Therefore, in this study, since higher durability was desired for the finishing materials fixed on the fabrics, nano-scaled hollow structured cyclodextrins were chemically imparted by grafting to the structure of conventional cotton fabrics by the help of finishing technique in order to be fixed permanently. By this way, a processed and functionalized base fabric having potential to be treated in the subsequent processes with many different finishing agents and nanomaterials could be obtained. Henceforth, this fabric can be used as a multi-functional fabric due to the encapturing ability of cyclodextrins to molecules/particles via physical/chemical means. In this study, scoured and rinsed woven bleached plain weave 100% cotton fabrics were utilized because textiles made of cotton are the most demanded textile products in the textile market by the textile consumers in daily life. Cotton fabric samples were immersed in treating baths containing β-cyclodextrin and 1,2,3,4-butanetetracarboxylic acid and to reduce the curing temperature the catalyst sodium hypophosphite monohydrate was used. All impregnated fabric samples were pre-dried. The reaction of grafting was performed in dry state. The treated and cured fabric samples were rinsed with warm distilled water and dried. The samples were dried for 4 h and weighed before and after finishing and rinsing. Stability and durability of β-cyclodextrins on fabric surface against external factors such as washing as well as strength of functionalized fabric in terms of tensile and tear strength were tested. Presence and homogeneity of distribution of β-cyclodextrins on fabric surface were characterized.

Modelling the Behavior of Commercial and Test Textiles against Laundering Process by Statistical Assessment of Their Performance

Various exterior factors have perpetual effects on textile materials during wear, use and laundering in everyday life. In accordance with their frequency of use, textile materials are required to be laundered at certain intervals. The medium in which the laundering process takes place have inevitable detrimental physical and chemical effects on textile materials caused by the unique parameters of the process inherently existing. Connatural structures of various textile materials result in many different physical, chemical and mechanical characteristics. Because of their specific structures, these materials have different behaviors against several exterior factors. By modeling the behavior of commercial and test textiles as group-wise against laundering process, it is possible to disclose the relation in between these two groups of materials, which will lead to better understanding of their behaviors in terms of similarities and differences against the washing parameters of the laundering. Thus, the goal of the current research is to examine the behavior of two groups of textile materials as commercial textiles and as test textiles towards the main washing machine parameters during laundering process such as temperature, load quantity, mechanical action and level of water amount by concentrating on shrinkage, pilling, sewing defects, collar abrasion, the other defects other than sewing, whitening and overall properties of textiles. In this study, cotton fabrics were preferred as commercial textiles due to the fact that garments made of cotton are the most demanded products in the market by the textile consumers in daily life. Full factorial experimental set-up was used to design the experimental procedure. All profiles always including all of the commercial and the test textiles were laundered for 20 cycles by commercial home laundering machine to investigate the effects of the chosen parameters. For the laundering process, a modified version of ‘‘IEC 60456 Test Method’’ was utilized. The amount of detergent was altered as 0.5% gram per liter depending on varying load quantity levels. Datacolor 650®, EMPA Photographic Standards for Pilling Test and visual examination were utilized to test and characterize the textiles. Furthermore, in the current study the relation in between commercial and test textiles in terms of their performance was deeply investigated by the help of statistical analysis performed by MINITAB® package program modeling their behavior against the parameters of the laundering process. In the experimental work, the behaviors of both groups of textiles towards washing machine parameters were visually and quantitatively assessed in dry state.

Application of Tocopherol as Antioxidant to Reduce Decomposition Process on Palm Oil Biodiesel

Biodiesel is one of the alternative fuels promising for substituting petrodiesel as energy source which has an advantage as it is sustainable and eco-friendly. Due to the raw material that tends to decompose during storage, biodiesel also has the same characteristic that tends to decompose during storage. Biodiesel decomposition will form higher acid value as the result of oxidation to double bond on a fatty acid compound on biodiesel. Thus, free fatty acid value could be used to evaluate degradation of biodiesel due to the oxidation process. High free fatty acid on biodiesel could impact on the engine performance. Decomposition of biodiesel due to oxidation reaction could prevent by introducing a small amount of antioxidant. The origin of raw materials and the process for producing biodiesel will determine the effectiveness of antioxidant. Biodiesel made from high free fatty acid (FFA) crude palm oil (CPO) by using two steps esterification is vulnerable to oxidation process which is resulted in increasing on the FFA value. Tocopherol also known as vitamin E is one of the antioxidant that could improve the stability of biodiesel due to decomposition by the oxidation process. Tocopherol 0.5% concentration on palm oil biodiesel could reduce 13% of increasing FFA under temperature 80 °C and exposing time 180 minute.

Removal of Lead from Aqueous Solutions by Biosorption on Pomegranate Skin: Kinetics, Equilibrium and Thermodynamics

In this study, pomegranate skin, a material suitable for the conditions in Algeria, was chosen as adsorbent material for removal of lead in an aqueous solution. Biosorption studies were carried out under various parameters such as mass adsorbent particle, pH, contact time, the initial concentration of metal, and temperature. The experimental results show that the percentage of biosorption increases with an increase in the biosorbent mass (0.25 g, 0.035 mg/g; 1.25 g, 0.096 mg/g). The maximum biosorption occurred at pH value of 8 for the lead. The equilibrium uptake was increased with an increase in the initial concentration of metal in solution (Co = 4 mg/L, qt = 1.2 mg/g). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The best fit was obtained by the Langmuir model with high correlation coefficients (R2 > 0.995) and a maximum monolayer adsorption capacity of 0.85 mg/g for lead. The adsorption of the lead was exothermic in nature (ΔH° = -17.833 kJ/mol for Pb (II). The reaction was accompanied by a decrease in entropy (ΔS° = -0.056 kJ/K. mol). The Gibbs energy (ΔG°) increased from -1.458 to -0.305 kJ/mol, respectively for Pb (II) when the temperature was increased from 293 to 313 K.

Equilibrium, Kinetic and Thermodynamic Studies of the Biosorption of Textile Dye (Yellow Bemacid) onto Brahea edulis

Environmental contamination is a major problem being faced by the society today. Industrial, agricultural, and domestic wastes, due to the rapid development in the technology, are discharged in the several receivers. Generally, this discharge is directed to the nearest water sources such as rivers, lakes, and seas. While the rates of development and waste production are not likely to diminish, efforts to control and dispose of wastes are appropriately rising. Wastewaters from textile industries represent a serious problem all over the world. They contain different types of synthetic dyes which are known to be a major source of environmental pollution in terms of both the volume of dye discharged and the effluent composition. From an environmental point of view, the removal of synthetic dyes is of great concern. Among several chemical and physical methods, adsorption is a promising technique due to the ease of use and low cost compared to other applications in the process of discoloration, especially if the adsorbent is inexpensive and readily available. The focus of the present study was to assess the potentiality of Brahea edulis (BE) for the removal of synthetic dye Yellow bemacid (YB) from aqueous solutions. The results obtained here may transfer to other dyes with a similar chemical structure. Biosorption studies were carried out under various parameters such as mass adsorbent particle, pH, contact time, initial dye concentration, and temperature. The biosorption kinetic data of the material (BE) was tested by the pseudo first-order and the pseudo-second-order kinetic models. Thermodynamic parameters including the Gibbs free energy ΔG, enthalpy ΔH, and entropy ΔS have revealed that the adsorption of YB on the BE is feasible, spontaneous, and endothermic. The equilibrium data were analyzed by using Langmuir, Freundlich, Elovich, and Temkin isotherm models. The experimental results show that the percentage of biosorption increases with an increase in the biosorbent mass (0.25 g: 12 mg/g; 1.5 g: 47.44 mg/g). The maximum biosorption occurred at around pH value of 2 for the YB. The equilibrium uptake was increased with an increase in the initial dye concentration in solution (Co = 120 mg/l; q = 35.97 mg/g). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The best fit was obtained by the Langmuir model with high correlation coefficient (R2 > 0.998) and a maximum monolayer adsorption capacity of 35.97 mg/g for YB.

Determination of Optical Constants of Semiconductor Thin Films by Ellipsometry

Ellipsometry is an optical method based on the study of the behavior of polarized light. The light reflected on a surface induces a change in the polarization state which depends on the characteristics of the material (complex refractive index and thickness of the different layers constituting the device). The purpose of this work is to determine the optical properties of semiconductor thin films by ellipsometry. This paper describes the experimental aspects concerning the semiconductor samples, the SE400 ellipsometer principle, and the results obtained by direct measurements of ellipsometric parameters and modelling using appropriate software.

Identifying Knowledge Gaps in Incorporating Toxicity of Particulate Matter Constituents for Developing Regulatory Limits on Particulate Matter

Regulatory bodies has proposed limits on Particulate Matter (PM) concentration in air; however, it does not explicitly indicate the incorporation of effects of toxicities of constituents of PM in developing regulatory limits. This study aimed to provide a structured approach to incorporate toxic effects of components in developing regulatory limits on PM. A four-step human health risk assessment framework consists of - (1) hazard identification (parameters: PM and its constituents and their associated toxic effects on health), (2) exposure assessment (parameters: concentrations of PM and constituents, information on size and shape of PM; fate and transport of PM and constituents in respiratory system), (3) dose-response assessment (parameters: reference dose or target toxicity dose of PM and its constituents), and (4) risk estimation (metric: hazard quotient and/or lifetime incremental risk of cancer as applicable). Then parameters required at every step were obtained from literature. Using this information, an attempt has been made to determine limits on PM using component-specific information. An example calculation was conducted for exposures of PM2.5 and its metal constituents from Indian ambient environment to determine limit on PM values. Identified data gaps were: (1) concentrations of PM and its constituents and their relationship with sampling regions, (2) relationship of toxicity of PM with its components.

Alumina Supported Cu-Mn-La Catalysts for CO and VOCs Oxidation

Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al2O3 supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH3OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La2O3, MnO2 and Cu1.5Mn1.5O4. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.

Phase Transition and Molecular Polarizability Studies in Liquid Crystalline Mixtures

In this work, two mixtures with equal concentrations of 1) 4ꞌ-(6-(4-(pentylamino) methyl)-3-hydroxyphenoxy) hexyloxy) biphenyl-4-carbonitrile+-4-((4-(hexyloxy) benzylidene) amino) phenyl 4-butoxy benzoate and 2) 4ꞌ - (6-(4-(hexylamino) methyl)-3-hydroxyphenoxy) hexyloxy) biphenyl-4-carbonitrile+-4-((4-(octyloxy) benzylidene) amino) phenyl 4-butoxy benzoate, have been prepared. The transition temperature and optical texture are observed by using thermal microscopy. Density and birefringence studies are carried out on the above liquid crystalline mixtures. Using density and refractive indices data, the molecular polarizabilities are evaluated by using well-known Vuks and Neugebauer models. The molecular polarizability is also evaluated theoretically by Lippincott δ function model. The results reveal that the polarizability values are same in both experimental and theoretical methods.

Screening of Factors Affecting the Enzymatic Hydrolysis of Empty Fruit Bunches in Aqueous Ionic Liquid and Locally Produced Cellulase System

The enzymatic hydrolysis of lignocellulosic biomass is one of the obstacles in the process of sugar production, due to the presence of lignin that protects the cellulose molecules against cellulases. Although the pretreatment of lignocellulose in ionic liquid (IL) system has been receiving a lot of interest; however, it requires IL removal with an anti-solvent in order to proceed with the enzymatic hydrolysis. At this point, introducing a compatible cellulase enzyme seems more efficient in this process. A cellulase enzyme that was produced by Trichoderma reesei on palm kernel cake (PKC) exhibited a promising stability in several ILs. The enzyme called PKC-Cel was tested for its optimum pH and temperature as well as its molecular weight. One among evaluated ILs, 1,3-diethylimidazolium dimethyl phosphate [DEMIM] DMP was applied in this study. Evaluation of six factors was executed in Stat-Ease Design Expert V.9, definitive screening design, which are IL/ buffer ratio, temperature, hydrolysis retention time, biomass loading, cellulase loading and empty fruit bunches (EFB) particle size. According to the obtained data, IL-enzyme system shows the highest sugar concentration at 70 °C, 27 hours, 10% IL-buffer, 35% biomass loading, 60 Units/g cellulase and 200 μm particle size. As concluded from the obtained data, not only the PKC-Cel was stable in the presence of the IL, also it was actually stable at a higher temperature than its optimum one. The reducing sugar obtained was 53.468±4.58 g/L which was equivalent to 0.3055 g reducing sugar/g EFB. This approach opens an insight for more studies in order to understand the actual effect of ILs on cellulases and their interactions in the aqueous system. It could also benefit in an efficient production of bioethanol from lignocellulosic biomass.

Fabrication of Powdery Composites Based Alumina and Its Consolidation by Hot Pressing Method in OXY-GON Furnace

In this work, obtaining methods of ultrafine alumina powdery composites and high temperature pressing technology of matrix ceramic composites with different compositions have been discussed. Alumina was obtained by solution combustion synthesis and sol-gel methods. Metal carbides containing powdery composites were obtained by homogenization of finishing powders in nanomills, as well as by their single-step high temperature synthesis .Different types of matrix ceramics composites (α-Al2O3-ZrO2-Y2O3, α-Al2O3- Y2O3-MgO, α-Al2O3-SiC-Y2O3, α-Al2O3-WC-Co-Y2O3, α-Al2O3- B4C-Y2O3, α-Al2O3- B4C-TiB2 etc.) were obtained by using OXYGON furnace. Consolidation of powders were carried out at 1550- 1750°C (hold time - 1 h, pressure - 50 MPa). Corundum ceramics samples have been obtained and characterized by high hardness and fracture toughness, absence of open porosity, high corrosion resistance. Their density reaches 99.5-99.6% TD. During the work, the following devices have been used: High temperature vacuum furnace OXY-GON Industries Inc (USA), Electronic Scanning Microscopes Nikon Eclipse LV 150, Optical Microscope NMM- 800TRF, Planetary mill Pulverisette 7 premium line, Shimadzu Dynamic Ultra Micro Hardness Tester DUH-211S, Analysette 12 Dynasizer.

Argon/Oxygen Plasma Surface Modification of Biopolymers for Improvement of Wettability and Wear Resistance

Artificial joint replacements such as total knee and total hip prosthesis have been applied to the patients who affected by osteoarthritis. Although different material combinations are used for these joints, biopolymers are most commonly preferred materials especially for acetabular cup and tibial component of hip and knee joints respectively. The main limitation that shortens the service life of these prostheses is wear. Wear is complicated phenomena and it must be considered with friction and lubrication. In this study, micro wave (MW) induced argon+oxygen plasma surface modification were applied on ultra-high molecular weight polyethylene (UHMWPE) and vitamin E blended UHMWPE (VE-UHMWPE) biopolymer surfaces to improve surface wettability and wear resistance of the surfaces. Contact angel measurement method was used for determination of wettability. Ball-on-disc wear test was applied under 25% bovine serum lubrication conditions. The results show that surface wettability and wear resistance of both material samples were increased by plasma surface modification.

Effects of Canned Cycles and Cutting Parameters on Hole Quality in Cryogenic Drilling of Aluminum 6061-6T

The influence of canned cycles and cutting parameters on hole quality in cryogenic drilling has been investigated experimentally and analytically. A three-level, three-parameter experiment was conducted by using the design-of-experiment methodology. The three levels of independent input parameters were the following: for canned cycles—a chip-breaking canned cycle (G73), a spot drilling canned cycle (G81), and a deep hole canned cycle (G83); for feed rates—0.2, 0.3, and 0.4 mm/rev; and for cutting speeds—60, 75, and 100 m/min. The selected work and tool materials were aluminum 6061-6T and high-speed steel (HSS), respectively. For cryogenic cooling, liquid nitrogen (LN2) was used and was applied externally. The measured output parameters were the three widely used quality characteristics of drilled holes—diameter error, circularity, and surface roughness. Pareto ANOVA was applied for analyzing the results. The findings revealed that the canned cycle has a significant effect on diameter error (contribution ratio 44.09%) and small effects on circularity and surface finish (contribution ratio 7.25% and 6.60%, respectively). The best results for the dimensional accuracy and surface roughness were achieved by G81. G73 produced the best circularity results; however, for dimensional accuracy, it was the worst level.

Ligandless Extraction and Determination of Trace Amounts of Lead in Pomegranate, Zucchini and Lettuce Samples after Dispersive Liquid-Liquid Microextraction with Ultrasonic Bath and Optimization of Extraction Condition with RSM Design

Heavy metals are released into water, plants, soil, and food by natural and human activities. Lead has toxic roles in the human body and may cause serious problems even in low concentrations, since it may have several adverse effects on human. Therefore, determination of lead in different samples is an important procedure in the studies of environmental pollution. In this work, an ultrasonic assisted-ionic liquid based-liquid-liquid microextraction (UA-IL-DLLME) procedure for the determination of lead in zucchini, pomegranate, and lettuce has been established and developed by using flame atomic absorption spectrometer (FAAS). For UA-IL-DLLME procedure, 10 mL of the sample solution containing Pb2+ was adjusted to pH=5 in a glass test tube with a conical bottom; then, 120 μL of 1-Hexyl-3-methylimidazolium hexafluoro phosphate (CMIM)(PF6) was rapidly injected into the sample solution with a microsyringe. After that, the resulting cloudy mixture was treated by ultrasonic for 5 min, then the separation of two phases was obtained by centrifugation for 5 min at 3000 rpm and IL-phase diluted with 1 cc ethanol, and the analytes were determined by FAAS. The effect of different experimental parameters in the extraction step including: ionic liquid volume, sonication time and pH was studied and optimized simultaneously by using Response Surface Methodology (RSM) employing a central composite design (CCD). The optimal conditions were determined to be an ionic liquid volume of 120 μL, sonication time of 5 min, and pH=5. The linear ranges of the calibration curve for the determination by FAAS of lead were 0.1-4 ppm with R2=0.992. Under optimized conditions, the limit of detection (LOD) for lead was 0.062 μg.mL-1, the enrichment factor (EF) was 93, and the relative standard deviation (RSD) for lead was calculated as 2.29%. The levels of lead for pomegranate, zucchini, and lettuce were calculated as 2.88 μg.g-1, 1.54 μg.g-1, 2.18 μg.g-1, respectively. Therefore, this method has been successfully applied for the analysis of the content of lead in different food samples by FAAS.

Improvement of Wear Resistance of 356 Aluminum Alloy by High Energy Electron Beam Irradiation

This study is concerned with the microstructural analysis and improvement of wear resistance of 356 aluminum alloy by a high energy electron beam. Shock hardening on material by high energy electron beam improved wear resistance. Particularly, in the surface of material by shock hardening, the wear resistance was greatly enhanced to 29% higher than that of the 356 aluminum alloy substrate. These findings suggested that surface shock hardening using high energy electron beam irradiation was economical and useful for the development of surface shock hardening with improved wear resistance.

Influence of Argon Gas Concentration in N2-Ar Plasma for the Nitridation of Si in Abnormal Glow Discharge

Nitriding of p-type Si samples by pulsed DC glow discharge is carried out for different Ar concentrations (30% to 90%) in nitrogen-argon plasma whereas the other parameters like pressure (2 mbar), treatment time (4 hr) and power (175 W) are kept constant. The phase identification, crystal structure, crystallinity, chemical composition, surface morphology and topography of the nitrided layer are studied using X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), optical microscopy (OM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) respectively. The XRD patterns reveal the development of different diffraction planes of Si3N4 confirming the formation of polycrystalline layer. FTIR spectrum confirms the formation of bond between Si and N. Results reveal that addition of Ar into N2 plasma plays an important role to enhance the production of active species which facilitate the nitrogen diffusion.

Influence of Boron Doping and Thermal Treatment on Internal Friction of Monocrystalline Si1-xGex(x≤0,02) Alloys

The impact of boron doping on the internal friction (IF) and shear modulus temperature spectra of Si1-xGex(x≤0,02) monocrsytals has been investigated by reverse torsional pendulum oscillations characteristics testing. At room temperatures, microhardness and indentation modulus of the same specimens have been measured by dynamic ultra microhardness tester. It is shown that boron doping causes two kinds effect: At low boron concentration (~1015 cm-3) significant strengthening is revealed, while at the high boron concentration (~1019 cm-3) strengthening effect and activation characteristics of relaxation origin IF processes are reduced.

Method and Experiment of Fabricating and Cutting the Burr for Y Shape Nanochannel

The present paper proposes using atomic force microscopy (AFM) and the concept of specific down force energy (SDFE) to establish a method for fabricating and cutting the burr for Y shape nanochannel on silicon (Si) substrate. For fabricating Y shape nanochannel, it first makes the experimental cutting path planning for fabricating Y shape nanochannel until the fifth cutting layer. Using the constant down force by AFM and SDFE theory and following the experimental cutting path planning, the cutting depth and width of each pass of Y shape nanochannel can be predicted by simulation. The paper plans the path for cutting the burr at the edge of Y shape nanochannel. Then, it carries out cutting the burr along the Y nanochannel edge by using a smaller down force. The height of standing burr at the edge is required to be below the set value of 0.54 nm. The results of simulation and experiment of fabricating and cutting the burr for Y shape nanochannel is further compared.