Search results for: beam–column joints
Commenced in January 2007
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Edition: International
Paper Count: 1959

Search results for: beam–column joints

9 Analytical Model of Locomotion of a Thin-Film Piezoelectric 2D Soft Robot Including Gravity Effects

Authors: Zhiwu Zheng, Prakhar Kumar, Sigurd Wagner, Naveen Verma, James C. Sturm

Abstract:

Soft robots have drawn great interest recently due to a rich range of possible shapes and motions they can take on to address new applications, compared to traditional rigid robots. Large-area electronics (LAE) provides a unique platform for creating soft robots by leveraging thin-film technology to enable the integration of a large number of actuators, sensors, and control circuits on flexible sheets. However, the rich shapes and motions possible, especially when interacting with complex environments, pose significant challenges to forming well-generalized and robust models necessary for robot design and control. In this work, we describe an analytical model for predicting the shape and locomotion of a flexible (steel-foil-based) piezoelectric-actuated 2D robot based on Euler-Bernoulli beam theory. It is nominally (unpowered) lying flat on the ground, and when powered, its shape is controlled by an array of piezoelectric thin-film actuators. Key features of the models are its ability to incorporate the significant effects of gravity on the shape and to precisely predict the spatial distribution of friction against the contacting surfaces, necessary for determining inchworm-type motion. We verified the model by developing a distributed discrete element representation of a continuous piezoelectric actuator and by comparing its analytical predictions to discrete-element robot simulations using PyBullet. Without gravity, predicting the shape of a sheet with a linear array of piezoelectric actuators at arbitrary voltages is straightforward. However, gravity significantly distorts the shape of the sheet, causing some segments to flatten against the ground. Our work includes the following contributions: (i) A self-consistent approach was developed to exactly determine which parts of the soft robot are lifted off the ground, and the exact shape of these sections, for an arbitrary array of piezoelectric voltages and configurations. (ii) Inchworm-type motion relies on controlling the relative friction with the ground surface in different sections of the robot. By adding torque-balance to our model and analyzing shear forces, the model can then determine the exact spatial distribution of the vertical force that the ground is exerting on the soft robot. Through this, the spatial distribution of friction forces between ground and robot can be determined. (iii) By combining this spatial friction distribution with the shape of the soft robot, in the function of time as piezoelectric actuator voltages are changed, the inchworm-type locomotion of the robot can be determined. As a practical example, we calculated the performance of a 5-actuator system on a 50-µm thick steel foil. Piezoelectric properties of commercially available thin-film piezoelectric actuators were assumed. The model predicted inchworm motion of up to 200 µm per step. For independent verification, we also modelled the system using PyBullet, a discrete-element robot simulator. To model a continuous thin-film piezoelectric actuator, we broke each actuator into multiple segments, each of which consisted of two rigid arms with appropriate mass connected with a 'motor' whose torque was set by the applied actuator voltage. Excellent agreement between our analytical model and the discrete-element simulator was shown for both for the full deformation shape and motion of the robot.

Keywords: analytical modeling, piezoelectric actuators, soft robot locomotion, thin-film technology

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8 Synthetic Method of Contextual Knowledge Extraction

Authors: Olga Kononova, Sergey Lyapin

Abstract:

Global information society requirements are transparency and reliability of data, as well as ability to manage information resources independently; particularly to search, to analyze, to evaluate information, thereby obtaining new expertise. Moreover, it is satisfying the society information needs that increases the efficiency of the enterprise management and public administration. The study of structurally organized thematic and semantic contexts of different types, automatically extracted from unstructured data, is one of the important tasks for the application of information technologies in education, science, culture, governance and business. The objectives of this study are the contextual knowledge typologization, selection or creation of effective tools for extracting and analyzing contextual knowledge. Explication of various kinds and forms of the contextual knowledge involves the development and use full-text search information systems. For the implementation purposes, the authors use an e-library 'Humanitariana' services such as the contextual search, different types of queries (paragraph-oriented query, frequency-ranked query), automatic extraction of knowledge from the scientific texts. The multifunctional e-library «Humanitariana» is realized in the Internet-architecture in WWS-configuration (Web-browser / Web-server / SQL-server). Advantage of use 'Humanitariana' is in the possibility of combining the resources of several organizations. Scholars and research groups may work in a local network mode and in distributed IT environments with ability to appeal to resources of any participating organizations servers. Paper discusses some specific cases of the contextual knowledge explication with the use of the e-library services and focuses on possibilities of new types of the contextual knowledge. Experimental research base are science texts about 'e-government' and 'computer games'. An analysis of the subject-themed texts trends allowed to propose the content analysis methodology, that combines a full-text search with automatic construction of 'terminogramma' and expert analysis of the selected contexts. 'Terminogramma' is made out as a table that contains a column with a frequency-ranked list of words (nouns), as well as columns with an indication of the absolute frequency (number) and the relative frequency of occurrence of the word (in %% ppm). The analysis of 'e-government' materials showed, that the state takes a dominant position in the processes of the electronic interaction between the authorities and society in modern Russia. The media credited the main role in these processes to the government, which provided public services through specialized portals. Factor analysis revealed two factors statistically describing the used terms: human interaction (the user) and the state (government, processes organizer); interaction management (public officer, processes performer) and technology (infrastructure). Isolation of these factors will lead to changes in the model of electronic interaction between government and society. In this study, the dominant social problems and the prevalence of different categories of subjects of computer gaming in science papers from 2005 to 2015 were identified. Therefore, there is an evident identification of several types of contextual knowledge: micro context; macro context; dynamic context; thematic collection of queries (interactive contextual knowledge expanding a composition of e-library information resources); multimodal context (functional integration of iconographic and full-text resources through hybrid quasi-semantic algorithm of search). Further studies can be pursued both in terms of expanding the resource base on which they are held, and in terms of the development of appropriate tools.

Keywords: contextual knowledge, contextual search, e-library services, frequency-ranked query, paragraph-oriented query, technologies of the contextual knowledge extraction

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7 Numerical Prediction of Width Crack of Concrete Dapped-End Beams

Authors: Jatziri Y. Moreno-Martinez, Arturo Galvan, Xavier Chavez Cardenas, Hiram Arroyo

Abstract:

Several methods have been utilized to study the prediction of cracking of concrete structural under loading. The finite element analysis is an alternative that shows good results. The aim of this work was the numerical study of the width crack in reinforced concrete beams with dapped ends, these are frequently found in bridge girders and precast concrete construction. Properly restricting cracking is an important aspect of the design in dapped ends, it has been observed that the cracks that exceed the allowable widths are unacceptable in an aggressive environment for reinforcing steel. For simulating the crack width, the discrete crack approach was considered by means of a Cohesive Zone (CZM) Model using a function to represent the crack opening. Two cases of dapped-end were constructed and tested in the laboratory of Structures and Materials of Engineering Institute of UNAM. The first case considers a reinforcement based on hangers as well as on vertical and horizontal ring, the second case considers 50% of the vertical stirrups in the dapped end to the main part of the beam were replaced by an equivalent area (vertically projected) of diagonal bars under. The loading protocol consisted on applying symmetrical loading to reach the service load. The models were performed using the software package ANSYS v. 16.2. The concrete structure was modeled using three-dimensional solid elements SOLID65 capable of cracking in tension and crushing in compression. Drucker-Prager yield surface was used to include the plastic deformations. The reinforcement was introduced with smeared approach. Interface delamination was modeled by traditional fracture mechanics methods such as the nodal release technique adopting softening relationships between tractions and the separations, which in turn introduce a critical fracture energy that is also the energy required to break apart the interface surfaces. This technique is called CZM. The interface surfaces of the materials are represented by a contact elements Surface-to-Surface (CONTA173) with bonded (initial contact). The Mode I dominated bilinear CZM model assumes that the separation of the material interface is dominated by the displacement jump normal to the interface. Furthermore, the opening crack was taken into consideration according to the maximum normal contact stress, the contact gap at the completion of debonding, and the maximum equivalent tangential contact stress. The contact elements were placed in the crack re-entrant corner. To validate the proposed approach, the results obtained with the previous procedure are compared with experimental test. A good correlation between the experimental and numerical Load-Displacement curves was presented, the numerical models also allowed to obtain the load-crack width curves. In these two cases, the proposed model confirms the capability of predicting the maximum crack width, with an error of ± 30 %. Finally, the orientation of the crack is a fundamental for the prediction of crack width. The results regarding the crack width can be considered as good from the practical point view. Load-Displacement curve of the test and the location of the crack were able to obtain favorable results.

Keywords: cohesive zone model, dapped-end beams, discrete crack approach, finite element analysis

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6 Optimized Electron Diffraction Detection and Data Acquisition in Diffraction Tomography: A Complete Solution by Gatan

Authors: Saleh Gorji, Sahil Gulati, Ana Pakzad

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Continuous electron diffraction tomography, also known as microcrystal electron diffraction (MicroED) or three-dimensional electron diffraction (3DED), is a powerful technique, which in combination with cryo-electron microscopy (cryo-ED), can provide atomic-scale 3D information about the crystal structure and composition of different classes of crystalline materials such as proteins, peptides, and small molecules. Unlike the well-established X-ray crystallography method, 3DED does not require large single crystals and can collect accurate electron diffraction data from crystals as small as 50 – 100 nm. This is a critical advantage as growing larger crystals, as required by X-ray crystallography methods, is often very difficult, time-consuming, and expensive. In most cases, specimens studied via 3DED method are electron beam sensitive, which means there is a limitation on the maximum amount of electron dose one can use to collect the required data for a high-resolution structure determination. Therefore, collecting data using a conventional scintillator-based fiber coupled camera brings additional challenges. This is because of the inherent noise introduced during the electron-to-photon conversion in the scintillator and transfer of light via the fibers to the sensor, which results in a poor signal-to-noise ratio and requires a relatively higher and commonly specimen-damaging electron dose rates, especially for protein crystals. As in other cryo-EM techniques, damage to the specimen can be mitigated if a direct detection camera is used which provides a high signal-to-noise ratio at low electron doses. In this work, we have used two classes of such detectors from Gatan, namely the K3® camera (a monolithic active pixel sensor) and Stela™ (that utilizes DECTRIS hybrid-pixel technology), to address this problem. The K3 is an electron counting detector optimized for low-dose applications (like structural biology cryo-EM), and Stela is also a counting electron detector but optimized for diffraction applications with high speed and high dynamic range. Lastly, data collection workflows, including crystal screening, microscope optics setup (for imaging and diffraction), stage height adjustment at each crystal position, and tomogram acquisition, can be one of the other challenges of the 3DED technique. Traditionally this has been all done manually or in a partly automated fashion using open-source software and scripting, requiring long hours on the microscope (extra cost) and extensive user interaction with the system. We have recently introduced Latitude® D in DigitalMicrograph® software, which is compatible with all pre- and post-energy-filter Gatan cameras and enables 3DED data acquisition in an automated and optimized fashion. Higher quality 3DED data enables structure determination with higher confidence, while automated workflows allow these to be completed considerably faster than before. Using multiple examples, this work will demonstrate how to direct detection electron counting cameras enhance 3DED results (3 to better than 1 Angstrom) for protein and small molecule structure determination. We will also show how Latitude D software facilitates collecting such data in an integrated and fully automated user interface.

Keywords: continuous electron diffraction tomography, direct detection, diffraction, Latitude D, Digitalmicrograph, proteins, small molecules

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5 Deep Learning Based on Image Decomposition for Restoration of Intrinsic Representation

Authors: Hyohun Kim, Dongwha Shin, Yeonseok Kim, Ji-Su Ahn, Kensuke Nakamura, Dongeun Choi, Byung-Woo Hong

Abstract:

Artefacts are commonly encountered in the imaging process of clinical computed tomography (CT) where the artefact refers to any systematic discrepancy between the reconstructed observation and the true attenuation coefficient of the object. It is known that CT images are inherently more prone to artefacts due to its image formation process where a large number of independent detectors are involved, and they are assumed to yield consistent measurements. There are a number of different artefact types including noise, beam hardening, scatter, pseudo-enhancement, motion, helical, ring, and metal artefacts, which cause serious difficulties in reading images. Thus, it is desired to remove nuisance factors from the degraded image leaving the fundamental intrinsic information that can provide better interpretation of the anatomical and pathological characteristics. However, it is considered as a difficult task due to the high dimensionality and variability of data to be recovered, which naturally motivates the use of machine learning techniques. We propose an image restoration algorithm based on the deep neural network framework where the denoising auto-encoders are stacked building multiple layers. The denoising auto-encoder is a variant of a classical auto-encoder that takes an input data and maps it to a hidden representation through a deterministic mapping using a non-linear activation function. The latent representation is then mapped back into a reconstruction the size of which is the same as the size of the input data. The reconstruction error can be measured by the traditional squared error assuming the residual follows a normal distribution. In addition to the designed loss function, an effective regularization scheme using residual-driven dropout determined based on the gradient at each layer. The optimal weights are computed by the classical stochastic gradient descent algorithm combined with the back-propagation algorithm. In our algorithm, we initially decompose an input image into its intrinsic representation and the nuisance factors including artefacts based on the classical Total Variation problem that can be efficiently optimized by the convex optimization algorithm such as primal-dual method. The intrinsic forms of the input images are provided to the deep denosing auto-encoders with their original forms in the training phase. In the testing phase, a given image is first decomposed into the intrinsic form and then provided to the trained network to obtain its reconstruction. We apply our algorithm to the restoration of the corrupted CT images by the artefacts. It is shown that our algorithm improves the readability and enhances the anatomical and pathological properties of the object. The quantitative evaluation is performed in terms of the PSNR, and the qualitative evaluation provides significant improvement in reading images despite degrading artefacts. The experimental results indicate the potential of our algorithm as a prior solution to the image interpretation tasks in a variety of medical imaging applications. This work was supported by the MISP(Ministry of Science and ICT), Korea, under the National Program for Excellence in SW (20170001000011001) supervised by the IITP(Institute for Information and Communications Technology Promotion).

Keywords: auto-encoder neural network, CT image artefact, deep learning, intrinsic image representation, noise reduction, total variation

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4 Al2O3-Dielectric AlGaN/GaN Enhancement-Mode MOS-HEMTs by Using Ozone Water Oxidization Technique

Authors: Ching-Sung Lee, Wei-Chou Hsu, Han-Yin Liu, Hung-Hsi Huang, Si-Fu Chen, Yun-Jung Yang, Bo-Chun Chiang, Yu-Chuang Chen, Shen-Tin Yang

Abstract:

AlGaN/GaN high electron mobility transistors (HEMTs) have been intensively studied due to their intrinsic advantages of high breakdown electric field, high electron saturation velocity, and excellent chemical stability. They are also suitable for ultra-violet (UV) photodetection due to the corresponding wavelengths of GaN bandgap. To improve the optical responsivity by decreasing the dark current due to gate leakage problems and limited Schottky barrier heights in GaN-based HEMT devices, various metal-oxide-semiconductor HEMTs (MOS-HEMTs) have been devised by using atomic layer deposition (ALD), molecular beam epitaxy (MBE), metal-organic chemical vapor deposition (MOCVD), liquid phase deposition (LPD), and RF sputtering. The gate dielectrics include MgO, HfO2, Al2O3, La2O3, and TiO2. In order to provide complementary circuit operation, enhancement-mode (E-mode) devices have been lately studied using techniques of fluorine treatment, p-type capper, piezoneutralization layer, and MOS-gate structure. This work reports an Al2O3-dielectric Al0.25Ga0.75N/GaN E-mode MOS-HEMT design by using a cost-effective ozone water oxidization technique. The present ozone oxidization method advantages of low cost processing facility, processing simplicity, compatibility to device fabrication, and room-temperature operation under atmospheric pressure. It can further reduce the gate-to-channel distance and improve the transocnductance (gm) gain for a specific oxide thickness, since the formation of the Al2O3 will consume part of the AlGaN barrier at the same time. The epitaxial structure of the studied devices was grown by using the MOCVD technique. On a Si substrate, the layer structures include a 3.9 m C-doped GaN buffer, a 300 nm GaN channel layer, and a 5 nm Al0.25Ga0.75N barrier layer. Mesa etching was performed to provide electrical isolation by using an inductively coupled-plasma reactive ion etcher (ICP-RIE). Ti/Al/Au were thermally evaporated and annealed to form the source and drain ohmic contacts. The device was immersed into the H2O2 solution pumped with ozone gas generated by using an OW-K2 ozone generator. Ni/Au were deposited as the gate electrode to complete device fabrication of MOS-HEMT. The formed Al2O3 oxide thickness 7 nm and the remained AlGaN barrier thickness is 2 nm. A reference HEMT device has also been fabricated in comparison on the same epitaxial structure. The gate dimensions are 1.2 × 100 µm 2 with a source-to-drain spacing of 5 μm for both devices. The dielectric constant (k) of Al2O3 was characterized to be 9.2 by using C-V measurement. Reduced interface state density after oxidization has been verified by the low-frequency noise spectra, Hooge coefficients, and pulse I-V measurement. Improved device characteristics at temperatures of 300 K-450 K have been achieved for the present MOS-HEMT design. Consequently, Al2O3-dielectric Al0.25Ga0.75N/GaN E-mode MOS-HEMTs by using the ozone water oxidization method are reported. In comparison with a conventional Schottky-gate HEMT, the MOS-HEMT design has demonstrated excellent enhancements of 138% (176%) in gm, max, 118% (139%) in IDS, max, 53% (62%) in BVGD, 3 (2)-order reduction in IG leakage at VGD = -60 V at 300 (450) K. This work is promising for millimeter-wave integrated circuit (MMIC) and three-terminal active UV photodetector applications.

Keywords: MOS-HEMT, enhancement mode, AlGaN/GaN, passivation, ozone water oxidation, gate leakage

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3 3D Non-Linear Analyses by Using Finite Element Method about the Prediction of the Cracking in Post-Tensioned Dapped-End Beams

Authors: Jatziri Y. Moreno-Martínez, Arturo Galván, Israel Enrique Herrera Díaz, José Ramón Gasca Tirado

Abstract:

In recent years, for the elevated viaducts in Mexico City, a construction system based on precast/pre-stressed concrete elements has been used, in which the bridge girders are divided in two parts by imposing a hinged support in sections where the bending moments that are originated by the gravity loads in a continuous beam are minimal. Precast concrete girders with dapped ends are a representative sample of a behavior that has complex configurations of stresses that make them more vulnerable to cracking due to flexure–shear interaction. The design procedures for ends of the dapped girders are well established and are based primarily on experimental tests performed for different configurations of reinforcement. The critical failure modes that can govern the design have been identified, and for each of them, the methods for computing the reinforcing steel that is needed to achieve adequate safety against failure have been proposed. Nevertheless, the design recommendations do not include procedures for controlling diagonal cracking at the entrant corner under service loading. These cracks could cause water penetration and degradation because of the corrosion of the steel reinforcement. The lack of visual access to the area makes it difficult to detect this damage and take timely corrective actions. Three-dimensional non-linear numerical models based on Finite Element Method to study the cracking at the entrant corner of dapped-end beams were performed using the software package ANSYS v. 11.0. The cracking was numerically simulated by using the smeared crack approach. The concrete structure was modeled using three-dimensional solid elements SOLID65 capable of cracking in tension and crushing in compression. Drucker-Prager yield surface was used to include the plastic deformations. The longitudinal post-tension was modeled using LINK8 elements with multilinear isotropic hardening behavior using von Misses plasticity. The reinforcement was introduced with smeared approach. The numerical models were calibrated using experimental tests carried out in “Instituto de Ingeniería, Universidad Nacional Autónoma de México”. In these numerical models the characteristics of the specimens were considered: typical solution based on vertical stirrups (hangers) and on vertical and horizontal hoops with a post-tensioned steel which contributed to a 74% of the flexural resistance. The post-tension is given by four steel wires with a 5/8’’ (16 mm) diameter. Each wire was tensioned to 147 kN and induced an average compressive stress of 4.90 MPa on the concrete section of the dapped end. The loading protocol consisted on applying symmetrical loading to reach the service load (180 kN). Due to the good correlation between experimental and numerical models some additional numerical models were proposed by considering different percentages of post-tension in order to find out how much it influences in the appearance of the cracking in the reentrant corner of the dapped-end beams. It was concluded that the increasing of percentage of post-tension decreases the displacements and the cracking in the reentrant corner takes longer to appear. The authors acknowledge at “Universidad de Guanajuato, Campus Celaya-Salvatierra” and the financial support of PRODEP-SEP (UGTO-PTC-460) of the Mexican government. The first author acknowledges at “Instituto de Ingeniería, Universidad Nacional Autónoma de México”.

Keywords: concrete dapped-end beams, cracking control, finite element analysis, postension

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2 Full Characterization of Heterogeneous Antibody Samples under Denaturing and Native Conditions on a Hybrid Quadrupole-Orbitrap Mass Spectrometer

Authors: Rowan Moore, Kai Scheffler, Eugen Damoc, Jennifer Sutton, Aaron Bailey, Stephane Houel, Simon Cubbon, Jonathan Josephs

Abstract:

Purpose: MS analysis of monoclonal antibodies (mAbs) at the protein and peptide levels is critical during development and production of biopharmaceuticals. The compositions of current generation therapeutic proteins are often complex due to various modifications which may affect efficacy. Intact proteins analyzed by MS are detected in higher charge states that also provide more complexity in mass spectra. Protein analysis in native or native-like conditions with zero or minimal organic solvent and neutral or weakly acidic pH decreases charge state value resulting in mAb detection at higher m/z ranges with more spatial resolution. Methods: Three commercially available mAbs were used for all experiments. Intact proteins were desalted online using size exclusion chromatography (SEC) or reversed phase chromatography coupled on-line with a mass spectrometer. For streamlined use of the LC- MS platform we used a single SEC column and alternately selected specific mobile phases to perform separations in either denaturing or native-like conditions: buffer A (20 % ACN, 0.1 % FA) with Buffer B (100 mM ammonium acetate). For peptide analysis mAbs were proteolytically digested with and without prior reduction and alkylation. The mass spectrometer used for all experiments was a commercially available Thermo Scientific™ hybrid Quadrupole-Orbitrap™ mass spectrometer, equipped with the new BioPharma option which includes a new High Mass Range (HMR) mode that allows for improved high mass transmission and mass detection up to 8000 m/z. Results: We have analyzed the profiles of three mAbs under reducing and native conditions by direct infusion with offline desalting and with on-line desalting via size exclusion and reversed phase type columns. The presence of high salt under denaturing conditions was found to influence the observed charge state envelope and impact mass accuracy after spectral deconvolution. The significantly lower charge states observed under native conditions improves the spatial resolution of protein signals and has significant benefits for the analysis of antibody mixtures, e.g. lysine variants, degradants or sequence variants. This type of analysis requires the detection of masses beyond the standard mass range ranging up to 6000 m/z requiring the extended capabilities available in the new HMR mode. We have compared each antibody sample that was analyzed individually with mixtures in various relative concentrations. For this type of analysis, we observed that apparent native structures persist and ESI is benefited by the addition of low amounts of acetonitrile and formic acid in combination with the ammonium acetate-buffered mobile phase. For analyses on the peptide level we analyzed reduced/alkylated, and non-reduced proteolytic digests of the individual antibodies separated via reversed phase chromatography aiming to retrieve as much information as possible regarding sequence coverage, disulfide bridges, post-translational modifications such as various glycans, sequence variants, and their relative quantification. All data acquired were submitted to a single software package for analysis aiming to obtain a complete picture of the molecules analyzed. Here we demonstrate the capabilities of the mass spectrometer to fully characterize homogeneous and heterogeneous therapeutic proteins on one single platform. Conclusion: Full characterization of heterogeneous intact protein mixtures by improved mass separation on a quadrupole-Orbitrap™ mass spectrometer with extended capabilities has been demonstrated.

Keywords: disulfide bond analysis, intact analysis, native analysis, mass spectrometry, monoclonal antibodies, peptide mapping, post-translational modifications, sequence variants, size exclusion chromatography, therapeutic protein analysis, UHPLC

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1 Improvement in the Photocatalytic Activity of Nanostructured Manganese Ferrite – Type of Materials by Mechanochemical Activation

Authors: Katerina Zaharieva, Katya Milenova, Zara Cherkezova-Zheleva, Alexander Eliyas, Boris Kunev, Ivan Mitov

Abstract:

The synthesized nanosized manganese ferrite-type of samples have been tested as photocatalysts in the reaction of oxidative degradation of model contaminant Reactive Black 5 (RB5) dye in aqueous solutions under UV irradiation. As it is known this azo dye is applied in the textile-coloring industry and it is discharged into the waterways causing pollution. The co-precipitation procedure has been used for the synthesis of manganese ferrite-type of materials: Sample 1 - Mn0.25Fe2.75O4, Sample 2 - Mn0.5Fe2.5O4 and Sample 3 - MnFe2O4 from 0.03M aqueous solutions of MnCl2•4H2O, FeCl2•4H2O and/or FeCl3•6H2O and 0.3M NaOH in appropriate amounts. The mechanochemical activation of co-precipitated ferrite-type of samples has been performed in argon (Samples 1 and 2) or in air atmosphere (Sample 3) for 2 hours at a milling speed of 500 rpm. The mechano-chemical treatment has been carried out in a high energy planetary ball mill type PM 100, Retsch, Germany. The mass ratio between balls and powder was 30:1. As a result mechanochemically activated Sample 4 - Mn0.25Fe2.75O4, Sample 5 - Mn0.5Fe2.5O4 and Sample 6 - MnFe2O4 have been obtained. The synthesized manganese ferrite-type photocatalysts have been characterized by X-ray diffraction method and Moessbauer spectroscopy. The registered X-ray diffraction patterns and Moessbauer spectra of co-precipitated ferrite-type of materials show the presence of manganese ferrite and additional akaganeite phase. The presence of manganese ferrite and small amounts of iron phases is established in the mechanochemically treated samples. The calculated average crystallite size of manganese ferrites varies within the range 7 – 13 nm. This result is confirmed by Moessbauer study. The registered spectra show superparamagnetic behavior of the prepared materials at room temperature. The photocatalytic investigations have been made using polychromatic UV-A light lamp (Sylvania BLB, 18 W) illumination with wavelength maximum at 365 nm. The intensity of light irradiation upon the manganese ferrite-type photocatalysts was 0.66 mW.cm-2. The photocatalytic reaction of oxidative degradation of RB5 dye was carried out in a semi-batch slurry photocatalytic reactor with 0.15 g of ferrite-type powder, 150 ml of 20 ppm dye aqueous solution under magnetic stirring at rate 400 rpm and continuously feeding air flow. The samples achieved adsorption-desorption equilibrium in the dark period for 30 min and then the UV-light was turned on. After regular time intervals aliquot parts from the suspension were taken out and centrifuged to separate the powder from solution. The residual concentrations of dye were established by a UV-Vis absorbance single beam spectrophotometer CamSpec M501 (UK) measuring in the wavelength region from 190 to 800 nm. The photocatalytic measurements determined that the apparent pseudo-first-order rate constants calculated by linear slopes approximating to first order kinetic equation, increase in following order: Sample 3 (1.1х10-3 min-1) < Sample 1 (2.2х10-3 min-1) < Sample 2 (3.3 х10-3 min-1) < Sample 4 (3.8х10-3 min-1) < Sample 6 (11х10-3 min-1) < Sample 5 (15.2х10-3 min-1). The mechanochemically activated manganese ferrite-type of photocatalyst samples show significantly higher degree of oxidative degradation of RB5 dye after 120 minutes of UV light illumination in comparison with co-precipitated ferrite-type samples: Sample 5 (92%) > Sample 6 (91%) > Sample 4 (63%) > Sample 2 (53%) > Sample 1 (42%) > Sample 3 (15%). Summarizing the obtained results we conclude that the mechanochemical activation leads to a significant enhancement of the degree of oxidative degradation of the RB5 dye and photocatalytic activity of tested manganese ferrite-type of catalyst samples under our experimental conditions. The mechanochemically activated Mn0.5Fe2.5O4 ferrite-type of material displays the highest photocatalytic activity (15.2х10-3 min-1) and degree of oxidative degradation of the RB5 dye (92%) compared to the other synthesized samples. Especially a significant improvement in the degree of oxidative degradation of RB5 dye (91%) has been determined for mechanochemically treated MnFe2O4 ferrite-type of sample with the highest extent of substitution of iron ions by manganese ions than in the case of the co-precipitated MnFe2O4 sample (15%). The mechanochemically activated manganese ferrite-type of samples show good photocatalytic properties in the reaction of oxidative degradation of RB5 azo dye in aqueous solutions and it could find potential application for dye removal from wastewaters originating from textile industry.

Keywords: nanostructured manganese ferrite-type materials, photocatalytic activity, Reactive Black 5, water treatment

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