Search results for: Sn doping in tellurium telluride nano-materials

Authors: Lidiia Nazarenko, Henryk Stolarski, Holm Altenbach

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In the paper, a (hierarchical) approach to analysis of thermo-elastic properties of random composites with interphases is outlined and illustrated. It is based on the statistical homogenization method – the method of conditional moments – combined with recently introduced notion of the energy-equivalent inhomogeneity which, in this paper, is extended to include thermal effects. After exposition of the general principles, the approach is applied in the investigation of the effective thermo-elastic properties of a material with randomly distributed nanoparticles. The basic idea of equivalent inhomogeneity is to replace the inhomogeneity and the surrounding it interphase by a single equivalent inhomogeneity of constant stiffness tensor and coefficient of thermal expansion, combining thermal and elastic properties of both. The equivalent inhomogeneity is then perfectly bonded to the matrix which allows to analyze composites with interphases using techniques devised for problems without interphases. From the mechanical viewpoint, definition of the equivalent inhomogeneity is based on Hill’s energy equivalence principle, applied to the problem consisting only of the original inhomogeneity and its interphase. It is more general than the definitions proposed in the past in that, conceptually and practically, it allows to consider inhomogeneities of various shapes and various models of interphases. This is illustrated considering spherical particles with two models of interphases, Gurtin-Murdoch material surface model and spring layer model. The resulting equivalent inhomogeneities are subsequently used to determine effective thermo-elastic properties of randomly distributed particulate composites. The effective stiffness tensor and coefficient of thermal extension of the material with so defined equivalent inhomogeneities are determined by the method of conditional moments. Closed-form expressions for the effective thermo-elastic parameters of a composite consisting of a matrix and randomly distributed spherical inhomogeneities are derived for the bulk and the shear moduli as well as for the coefficient of thermal expansion. Dependence of the effective parameters on the interphase properties is included in the resulting expressions, exhibiting analytically the nature of the size-effects in nanomaterials. As a numerical example, the epoxy matrix with randomly distributed spherical glass particles is investigated. The dependence of the effective bulk and shear moduli, as well as of the effective thermal expansion coefficient on the particle volume fraction (for different radii of nanoparticles) and on the radius of nanoparticle (for fixed volume fraction of nanoparticles) for different interphase models are compared to and discussed in the context of other theoretical predictions. Possible applications of the proposed approach to short-fiber composites with various types of interphases are discussed.

Keywords: effective properties, energy equivalence, Gurtin-Murdoch surface model, interphase, random composites, spherical equivalent inhomogeneity, spring layer model

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Authors: Sundaram Chandrasekaran, Seung Hyun Hur

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Exploring strategies for oxygen vacancy engineering under mild conditions and understanding the relationship between dislocations and photoelectrochemical (PEC) cell performance are challenging issues for designing high performance PEC devices. Therefore, it is very important to understand that how the oxygen vacancies (VO) or other defect states affect the performance of the photocatalyst in photoelectric transfer. So far, it has been found that defects in nano or micro crystals can have two possible significances on the PEC performance. Firstly, an electron-hole pair produced at the interface of photoelectrode and electrolyte can recombine at the defect centers under illumination of light, thereby reducing the PEC performances. On the other hand, the defects could lead to a higher light absorption in the longer wavelength region and may act as energy centers for the water splitting reaction that can improve the PEC performances. Even if the dislocation growth of ZnO has been verified by the full density functional theory (DFT) calculations and local density approximation calculations (LDA), it requires further studies to correlate the structures of ZnO and PEC performances. Exploring the hybrid structures composed of graphene oxide (GO) and ZnO nanostructures offer not only the vision of how the complex structure form from a simple starting materials but also the tools to improve PEC performances by understanding the underlying mechanisms of mutual interactions. As there are few studies for the ZnO growth with other materials and the growth mechanism in those cases has not been clearly explored yet, it is very important to understand the fundamental growth process of nanomaterials with the specific materials, so that rational and controllable syntheses of efficient ZnO-based hybrid materials can be designed to prepare nanostructures that can exhibit significant PEC performances. Herein, we fabricated various ZnO nanostructures such as hollow sphere, bucky bowl, nanorod and triangle, investigated their pH dependent growth mechanism, and correlated the PEC performances with them. Especially, the origin of well-controlled dislocation-driven growth and its transformation mechanism of ZnO nanorods to triangles on the GO surface were discussed in detail. Surprisingly, the addition of GO during the synthesis process not only tunes the morphology of ZnO nanocrystals and also creates more oxygen vacancies (oxygen defects) in the lattice of ZnO, which obviously suggest that the oxygen vacancies be created by the redox reaction between GO and ZnO in which the surface oxygen is extracted from the surface of ZnO by the functional groups of GO. On the basis of our experimental and theoretical analysis, the detailed mechanism for the formation of specific structural shapes and oxygen vacancies via dislocation, and its impact in PEC performances are explored. In water splitting performance, the maximum photocurrent density of GO-ZnO triangles was 1.517mA/cm-2 (under UV light ~ 360 nm) vs. RHE with high incident photon to current conversion Efficiency (IPCE) of 10.41%, which is the highest among all samples fabricated in this study and also one of the highest IPCE reported so far obtained from GO-ZnO triangular shaped photocatalyst.

Keywords: dislocation driven growth, zinc oxide, graphene oxide, water splitting

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Authors: Xuechun Kan, Dongdong Li, Fan Li, Peidang Liu

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Triple-negative breast cancer (TNBC) is the most malignant subtype of breast cancer with a poor prognosis, and radiotherapy is one of the main treatment methods. However, due to the obvious resistance of tumor cells to radiotherapy, high dose of ionizing radiation is required during radiotherapy, which causes serious damage to normal tissues near the tumor. Therefore, how to improve radiotherapy resistance and enhance the specific killing of tumor cells by radiation is a hot issue that needs to be solved in clinic. Recent studies have shown that silver-based nanoparticles have strong radiosensitization, and silver nanoclusters (AgNCs) also provide a broad prospect for tumor targeted radiosensitization therapy due to their ultra-small size, low toxicity or non-toxicity, self-fluorescence and strong photostability. Aptamer 5TR1 is a 25-base oligonucleotide aptamer that can specifically bind to mucin-1 highly expressed on the membrane surface of TNBC 4T1 cells, and can be used as a highly efficient tumor targeting molecule. In this study, AgNCs were synthesized by DNA template based on 5TR1 aptamer (NC-T5-5TR1), and its role as a targeted radiosensitizer in TNBC radiotherapy was investigated. The optimal DNA template was first screened by fluorescence emission spectroscopy, and NC-T5-5TR1 was prepared. NC-T5-5TR1 was characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and dynamic light scattering. The inhibitory effect of NC-T5-5TR1 on cell activity was evaluated using the MTT method. Laser confocal microscopy was employed to observe NC-T5-5TR1 targeting 4T1 cells and verify its self-fluorescence characteristics. The uptake of NC-T5-5TR1 by 4T1 cells was observed by dark-field imaging, and the uptake peak was evaluated by inductively coupled plasma mass spectrometry. The radiation sensitization effect of NC-T5-5TR1 was evaluated through cell cloning and in vivo anti-tumor experiments. Annexin V-FITC/PI double staining flow cytometry was utilized to detect the impact of nanomaterials combined with radiotherapy on apoptosis. The results demonstrated that the particle size of NC-T5-5TR1 is about 2 nm, and the UV-visible absorption spectrum detection verifies the successful construction of NC-T5-5TR1, and it shows good dispersion. NC-T5-5TR1 significantly inhibited the activity of 4T1 cells and effectively targeted and fluoresced within 4T1 cells. The uptake of NC-T5-5TR1 reached its peak at 3 h in the tumor area. Compared with AgNCs without aptamer modification, NC-T5-5TR1 exhibited superior radiation sensitization, and combined radiotherapy significantly inhibited the activity of 4T1 cells and tumor growth in 4T1-bearing mice. The apoptosis level of NC-T5-5TR1 combined with radiation was significantly increased. These findings provide important theoretical and experimental support for NC-T5-5TR1 as a radiation sensitizer for TNBC.

Keywords: 5TR1 aptamer, silver nanoclusters, radio sensitization, triple-negative breast cancer

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Authors: Zhaoyang Liu, Detao Qin, Darren Delai Sun

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The onshore production of oil and gas (for example, shale gas) generates large quantities of wastewater, referred to be ‘produced water’, which contains high contents of oils and salts. The direct discharge of produced water, if not appropriately treated, can be toxic to the environment and human health. Membrane filtration has been deemed as an environmental-friendly and cost-effective technology for treating oily wastewater. However, conventional polymeric membranes have their drawbacks of either low salt rejection rate or high membrane fouling tendency when treating oily wastewater. Recent years, forward osmosis (FO) membrane filtration has emerged as a promising technology with its unique advantages of low operation pressure and less membrane fouling tendency. However, until now there is still no report about FO membranes specially designed and fabricated for treating the oily and salty produced water. In this study, a novel nanocomposite FO membrane was developed specially for treating oil- and salt-polluted produced water. By leveraging the recent advance of nanomaterials and nanotechnology, this nanocomposite FO membrane was designed to be made of double layers: an underwater oleophobic selective layer on top of a nanomaterial infused polymeric support layer. Wherein, graphene oxide (GO) nanosheets were selected to add into the polymeric support layer because adding GO nanosheets can optimize the pore structures of the support layer, thus potentially leading to high water flux for FO membranes. In addition, polyvinyl alcohol (PVA) hydrogel was selected as the selective layer because hydrated and chemically-crosslinked PVA hydrogel is capable of simultaneously rejecting oil and salt. After nanocomposite FO membranes were fabricated, the membrane structures were systematically characterized with the instruments of TEM, FESEM, XRD, ATR-FTIR, surface zeta-potential and Contact angles (CA). The membrane performances for treating produced waters were tested with the instruments of TOC, COD and Ion chromatography. The working mechanism of this new membrane was also analyzed. Very promising experimental results have been obtained. The incorporation of GO nanosheets can reduce internal concentration polarization (ICP) effect in the polymeric support layer. The structural parameter (S value) of the new FO membrane is reduced by 23% from 265 ± 31 μm to 205 ± 23 μm. The membrane tortuosity (τ value) is decreased by 20% from 2.55 ± 0.19 to 2.02 ± 0.13 μm, which contributes to the decrease of S value. Moreover, the highly-hydrophilic and chemically-cross-linked hydrogel selective layer present high antifouling property under saline oil/water emulsions. Compared with commercial FO membrane, this new FO membrane possesses three times higher water flux, higher removal efficiencies for oil (>99.9%) and salts (>99.7% for multivalent ions), and significantly lower membrane fouling tendency (<10%). To our knowledge, this is the first report of a nanocomposite FO membrane with the combined merits of high salt rejection, high oil repellency and high water flux for treating onshore oil/gas produced waters. Due to its outstanding performance and ease of fabrication, this novel nanocomposite FO membrane possesses great application potential in wastewater treatment industry.

Keywords: nanocomposite, membrane, polymer, graphene oxide

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Authors: S. A. Krutovertsev, A. E. Tarasova, L. S. Krutovertseva, O. M. Ivanova

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The aim of the work was to get stable sensitive films with good sensitivity to ethanolamine (C2H7NO) in air. Ethanolamine is used as adsorbent in different processes of gas purification and separation. Besides it has wide industrial application. Chemical sensors of sorption type are widely used for gas analysis. Their behavior is determined by sensor characteristics of sensitive sorption layer. Forming conditions and characteristics of chemical gas sensors based on nanostructured modified silica films activated by different admixtures have been studied. As additives molybdenum containing polyoxometalates of the eighteen series were incorporated in silica films. The method of hydrolythic polycondensation from tetraethyl orthosilicate solutions was used for forming such films in this work. The method’s advantage is a possibility to introduce active additives directly into an initial solution. This method enables to obtain sensitive thin films with high specific surface at room temperature. Particular properties make polyoxometalates attractive as active additives for forming of gas-sensitive films. As catalyst of different redox processes, they can either accelerate the reaction of the matrix with analyzed gas or interact with it, and it results in changes of matrix’s electrical properties Polyoxometalates based films were deposited on the test structures manufactured by microelectronic planar technology with interdigitated electrodes. Modified silica films were deposited by a casting method from solutions based on tetraethyl orthosilicate and polyoxometalates. Polyoxometalates were directly incorporated into initial solutions. Composite nanostructured films were deposited by drop casting method on test structures with a pair of interdigital metal electrodes formed at their surface. The sensor’s active area was 4.0 x 4.0 mm, and electrode gap was egual 0.08 mm. Morphology of the layers surface were studied with Solver-P47 scanning probe microscope (NT-MDT, Russia), the infrared spectra were investigated by a Bruker EQUINOX 55 (Germany). The conditions of film formation varied during the tests. Electrical parameters of the sensors were measured electronically in real-time mode. Films had highly developed surface with value of 450 m2/g and nanoscale pores. Thickness of them was 0,2-0,3 µm. The study shows that the conditions of the environment affect markedly the sensors characteristics, which can be improved by choosing of the right procedure of forming and processing. Addition of polyoxometalate into silica film resulted in stabilization of film mass and changed markedly of electrophysical characteristics. Availability of Mn3P2Mo18O62 into silica film resulted in good sensitivity and selectivity to ethanolamine. Sensitivity maximum was observed at weight content of doping additive in range of 30–50% in matrix. With ethanolamine concentration changing from 0 to 100 ppm films’ conductivity increased by 10-12 times. The increase of sensor’s sensitivity was received owing to complexing reaction of tested substance with cationic part of polyoxometalate. This fact results in intramolecular redox reaction which sharply change electrophysical properties of polyoxometalate. This process is reversible and takes place at room temperature.

Keywords: ethanolamine, gas analysis, polyoxometalate, silica film

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Authors: T. N. Tran Thi, J. Morse, C. Detlefs, P. K. Cook, C. Yıldırım, A. C. Jakobsen, T. Zhou, J. Hartwig, V. Zurbig, D. Caliste, B. Fernandez, D. Eon, O. Loto, M. L. Hicks, A. Pakpour-Tabrizi, J. Baruchel

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The ability to grow boron-doped diamond epilayers of high crystalline quality is a prerequisite for the fabrication of diamond power electronic devices, in particular high voltage diodes and metal-oxide-semiconductor (MOS) transistors. Boron and intrinsic diamond layers are homoepitaxially overgrown by microwave assisted chemical vapour deposition (MWCVD) on single crystal high pressure, high temperature (HPHT) grown bulk diamond substrates. Various epilayer thicknesses were grown, with dopant concentrations ranging from 1021 atom/cm³ at nanometer thickness in the case of 'delta doping', up 1016 atom/cm³ and 50µm thickness or high electric field drift regions. The crystalline quality of these overgrown layers as regards defects, strain, distortion… is critical for the device performance through its relation to the final electrical properties (Hall mobility, breakdown voltage...). In addition to the optimization of the epilayer growth conditions in the MWCVD reactor, other important questions related to the crystalline quality of the overgrown layer(s) are: 1) what is the dependence on the bulk quality and surface preparation methods of the HPHT diamond substrate? 2) how do defects already present in the substrate crystal propagate into the overgrown layer; 3) what types of new defects are created during overgrowth, what are their growth mechanisms, and how can these defects be avoided? 4) how can we relate in a quantitative manner parameters related to the measured crystalline quality of the boron doped layer to the electronic properties of final processed devices? We describe synchrotron-based techniques developed to address these questions. These techniques allow the visualization of local defects and crystal distortion which complements the data obtained by other well-established analysis methods such as AFM, SIMS, Hall conductivity…. We have used Grazing Incidence X-ray Diffraction (GIXRD) at the ID01 beamline of the ESRF to study lattice parameters and damage (strain, tilt and mosaic spread) both in diamond substrate near surface layers and in thick (10–50 µm) overgrown boron doped diamond epi-layers. Micro- and nano-section topography have been carried out at both the BM05 and ID06-ESRF) beamlines using rocking curve imaging techniques to study defects which have propagated from the substrate into the overgrown layer(s) and their influence on final electronic device performance. These studies were performed using various commercially sourced HPHT grown diamond substrates, with the MWCVD overgrowth carried out at the Fraunhofer IAF-Germany. The synchrotron results are in good agreement with low-temperature (5°K) cathodoluminescence spectroscopy carried out on the grown samples using an Inspect F5O FESEM fitted with an IHR spectrometer.

Keywords: synchrotron X-ray diffaction, crystalline quality, defects, diamond overgrowth, rocking curve imaging

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Authors: Nodar Kekelidze, David Kekelidze, Elza Khutsishvili, Bela Kvirkvelia

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The semiconductor devices are irreplaceable elements for investigations in Space (artificial Earth satellite, interplanetary space craft, probes, rockets) and for investigation of elementary particles on accelerators, for atomic power stations, nuclear reactors, robots operating on heavily radiation contaminated territories (Chernobyl, Fukushima). Unfortunately, the most important parameters of semiconductors dramatically worsen under irradiation. So creation of radiation-resistant semiconductor materials for opto and microelectronic devices is actual problem, as well as investigation of complicated processes developed in irradiated solid states. Homogeneous single crystals of InP-InAs solid solutions were grown with zone melting method. There has been studied the dependence of the optical absorption coefficient vs photon energy near fundamental absorption edge. This dependence changes dramatically with irradiation. The experiments were performed on InP, InAs and InP-InAs solid solutions before and after irradiation with electrons and fast neutrons. The investigations of optical properties were carried out on infrared spectrophotometer in temperature range of 10K-300K and 1mkm-50mkm spectral area. Radiation fluencies of fast neutrons was equal to 2·1018neutron/cm2 and electrons with 3MeV, 50MeV up to fluxes of 6·1017electron/cm2. Under irradiation, there has been revealed the exponential type of the dependence of the optical absorption coefficient vs photon energy with energy deficiency. The indicated phenomenon takes place at high and low temperatures as well at impurity different concentration and practically in all cases of irradiation by various energy electrons and fast neutrons. We have developed the common mechanism of this phenomenon for unirradiated materials and implemented the quantitative calculations of distinctive parameter; this is in a satisfactory agreement with experimental data. For the irradiated crystals picture get complicated. In the work, the corresponding analysis is carried out. It has been shown, that in the case of InP, irradiated with electrons (Ф=1·1017el/cm2), the curve of optical absorption is shifted to lower energies. This is caused by appearance of the tails of density of states in forbidden band due to local fluctuations of ionized impurity (defect) concentration. Situation is more complicated in the case of InAs and for solid solutions with composition near to InAs when besides noticeable phenomenon there takes place Burstein effect caused by increase of electrons concentration as a result of irradiation. We have shown, that in certain conditions it is possible the prevalence of Burstein effect. This causes the opposite effect: the shift of the optical absorption edge to higher energies. So in given solid solutions there take place two different opposite directed processes. By selection of solid solutions composition and doping impurity we obtained such InP-InAs, solid solution in which under radiation mutual compensation of optical absorption curves displacement occurs. Obtained result let create on the base of InP-InAs, solid solution radiation-resistant optical materials. Conclusion: It was established the nature of optical absorption near fundamental edge in semiconductor materials and it was created radiation-resistant optical material.

Keywords: InAs-InP, electrons concentration, irradiation, solid solutions

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Authors: Monisha Elumalai, Joana Guerreiro, Joana Carvalho, Marta Prado

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DNA biosensors popularity has been increasing over the past few years. Traditional analytical techniques tend to require complex steps and expensive equipment however DNA biosensors have the advantage of getting simple, fast and economic. Additionally, the combination of DNA biosensors with nanomaterials offers the opportunity to improve the selectivity, sensitivity and the overall performance of the devices. DNA biosensors are based on oligonucleotides as sensing elements. These oligonucleotides are highly specific to complementary DNA sequences resulting in the hybridization of the strands. DNA biosensors are not only an advantage in the clinical field but also applicable in numerous research areas such as food analysis or environmental control. Zebra Mussels (ZM), Dreissena polymorpha are invasive species responsible for enormous negative impacts on the environment and ecosystems. Generally, the detection of ZM is made when the observation of adult or macroscopic larvae's is made however at this stage is too late to avoid the harmful effects. Therefore, there is a need to develop an analytical tool for the early detection of ZM. Here, we present a portable plasmonic biosensor for the detection of environmental DNA (eDNA) released to the environment from this invasive species. The plasmonic DNA biosensor combines gold nanoparticles, as transducer elements, due to their great optical properties and high sensitivity. The detection strategy is based on the immobilization of a short base pair DNA sequence on the nanoparticles surface followed by specific hybridization in the presence of a complementary target DNA. The hybridization events are tracked by the optical response provided by the nanospheres and their surrounding environment. The identification of the DNA sequences (synthetic target and probes) to detect Zebra mussel were designed by using Geneious software in order to maximize the specificity. Moreover, to increase the optical response enzyme amplification of DNA might be used. The gold nanospheres were synthesized and characterized by UV-visible spectrophotometry and transmission electron microscopy (TEM). The obtained nanospheres present the maximum localized surface plasmon resonance (LSPR) peak position are found to be around 519 nm and a diameter of 17nm. The DNA probes modified with a sulfur group at one end of the sequence were then loaded on the gold nanospheres at different ionic strengths and DNA probe concentrations. The optimal DNA probe loading will be selected based on the stability of the optical signal followed by the hybridization study. Hybridization process leads to either nanoparticle dispersion or aggregation based on the presence or absence of the target DNA. Finally, this detection system will be integrated into an optical sensing platform. Considering that the developed device will be used in the field, it should fulfill the inexpensive and portability requirements. The sensing devices based on specific DNA detection holds great potential and can be exploited for sensing applications in-loco.

Keywords: ZM DNA, DNA probes, nicking enzyme, gold nanoparticles

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Authors: Piotr Jablonski, Krzysztof Mars, Wiktor Niemiec, Agnieszka Kyziol, Marek Hebda, Halina Krawiec, Karol Kyziol

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NiTi alloys, possessing unique mechanical properties such as pseudoelasticity and shape memory effect (SME), are suitable for many applications, including implanthology and biomedical devices. Additionally, these alloys have similar values of elastic modulus to those of human bones, what is very important in orthopedics. Unfortunately, the environment of physiological fluids in vivo causes unfavorable release of Ni ions, which in turn may lead to metalosis as well as allergic reactions and toxic effects in the body. For these reasons, the surface properties of NiTi alloys should be improved to increase corrosion resistance, taking into account biological properties, i.e. excellent biocompatibility. The prospective in this respect are layers based on DLC (Diamond-Like Carbon) structures, which are an attractive solution for many applications in implanthology. These coatings (DLC), usually obtained by PVD (Physical Vapour Deposition) and PA CVD (Plasma Activated Chemical Vapour Deposition) methods, can be also modified by doping with other elements like silicon, nitrogen, oxygen, fluorine, titanium and silver. These methods, in combination with a suitably designed structure of the layers, allow the possibility co-decide about physicochemical and biological properties of modified surfaces. Mentioned techniques provide specific physicochemical properties of substrates surface in a single technological process. In this work, the following types of layers based on DLC structures (incl. Si-DLC or Si/N-DLC) were proposed as prospective and attractive approach in surface functionalization of shape memory alloy. Nitinol substrates were modified in plasma conditions, using RF CVD (Radio Frequency Chemical Vapour Deposition). The influence of plasma treatment on the useful properties of modified substrates after deposition DLC layers doped with silica and/or nitrogen atoms, as well as only pre-treated in O2 NH3 plasma atmosphere in a RF reactor was determined. The microstructure and topography of the modified surfaces were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Furthermore, the atomic structure of coatings was characterized by IR and Raman spectroscopy. The research also included the evaluation of surface wettability, surface energy as well as the characteristics of selected mechanical and biological properties of the layers. In addition, the corrosion properties of alloys after and before modification in the physiological saline were also investigated. In order to determine the corrosion resistance of NiTi in the Ringer solution, the potentiodynamic polarization curves (LSV – Linear Sweep Voltamperometry) were plotted. Furthermore, the evolution of corrosion potential versus immersion time of TiNi alloy in Ringer solution was performed. Based on all carried out research, the usefullness of proposed modifications of nitinol for medical applications was assessed. It was shown, inter alia, that the obtained Si-DLC layers on the surface of NiTi alloy exhibit a characteristic complex microstructure, increased surface development, which is an important aspect in improving the osteointegration of an implant. Furthermore, the modified alloy exhibits biocompatibility, the transfer of the metal (Ni, Ti) to Ringer’s solution is clearly limited.

Keywords: bioactive coatings, corrosion resistance, doped DLC structure, NiTi alloy, RF CVD

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Authors: Sudip Kumar Sinha, Saptarshi Ghosh

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While there’s a perpetual buzz around zinc oxide (ZnO) superstructures for their unique optical features, the versatile material has been constantly utilized to manifest tailored electronic properties through rendition of distinct morphologies. And yet, the unorthodox approach of implementing the novel 1D nanostructures of ZnO (pristine or doped) for volatile sensing applications has ample scope to accommodate new unconventional morphologies. In the last two decades, solid-state sensors have attracted much curiosity for their relevance in identifying pollutant, toxic and other industrial gases. In particular gas sensors based on metal oxide semiconducting (wide Eg) nanomaterials have recently attracted intensive attention owing to their high sensitivity and fast response and recovery time. These materials when exposed to air, the atmospheric O2 dissociates and get absorb on the surface of the sensors by trapping the outermost shell electrons. Finally a depleted zone on the surface of the sensors is formed, that enhances the potential barrier height at grain boundary . Once a target gas is exposed to the sensor, the chemical interaction between the chemisorbed oxygen and the specific gas liberates the trapped electrons. Therefore altering the amount of adsorbate is a considerable approach to improve the sensitivity of any target gas/vapour molecule. Likewise, this study presents a spontaneous but self catalytic creation of Sn-doped ZnO hexagonal nanoprisms on Si (100) substrates through thermal evaporation-condensation method, and their subsequent deployment for volatile sensing. In particular, the sensors were utilized to detect molecules of ethanol, acetone and ammonia below their permissible exposure limits which returned sensitivities of around 85%, 80% and 50% respectively. The influence of Sn concentration on the growth, microstructural and optical properties of the nanoprisms along with its role in augmenting the sensing parameters has been detailed. The single-crystalline nanostructures have a typical diameter ranging from 300 to 500 nm and a length that extends up to few micrometers. HRTEM images confirmed the hexagonal crystallography for the nanoprisms, while SAED pattern asserted the single crystalline nature. The growth habit is along the low index <0001>directions. It has been seen that the growth mechanism of the as-deposited nanostructures are directly influenced by varying supersaturation ratio, fairly high substrate temperatures, and specified surface defects in certain crystallographic planes, all acting cooperatively decide the final product morphology. Room temperature photoluminescence (PL) spectra of this rod like structures exhibits a weak ultraviolet (UV) emission peak at around 380 nm and a broad green emission peak in the 505 nm regime. An estimate of the sensing parameters against dispensed target molecules highlighted the potential for the nanoprisms as an effective volatile sensing material. The Sn-doped ZnO nanostructures with unique prismatic morphology may find important applications in various chemical sensors as well as other potential nanodevices.

Keywords: gas sensor, HRTEM, photoluminescence, ultraviolet, zinc oxide

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Authors: Zeyu Zhou, Ziyu Zhao, Xiaochen Yang, Ling AI, Heng Zhai, Stuart Holmes

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As a promising sustainable alternative to traditional fossil fuels, fuel cell technology is highly favoured due to its enhanced working efficiency and reduced emissions. In the context of high-temperature fuel cells (operating above 100 °C), the most commonly used proton exchange membrane (PEM) is the Polybenzimidazole (PBI) doped phosphoric acid (PA) membrane. Grafting is a promising strategy to advance PA-doped PBI PEM technology. The existing grafting modification on PBI PEMs mainly focuses on grafting phosphate-containing or alkaline groups onto the PBI molecular chains. However, quaternary ammonium-based grafting approaches face a common challenge. To initiate the N-alkylation reaction, deacidifying agents such as NaH, NaOH, KOH, K2CO3, etc., can lead to ionic crosslinking between the quaternary ammonium group and PBI. Polyvinylpyrrolidone (PVP) is another widely used polymer, the N-heterocycle groups within PVP endow it with a significant ability to absorb PA. Recently, PVP has attracted substantial attention in the field of fuel cells due to its reduced environmental impact and impressive fuel cell performance. However, due to the the poor compatibility of PVP in PBI, few research apply PVP in PA-doped PBI PEMs. This work introduces an innovative strategy to graft PVP onto PBI to form a network-like polymer. Due to the absence of quaternary ammonium groups, PVP does not pose issues related to crosslinking with PBI. Moreover, the nitrogen-containing functional groups on PVP provide PBI with a robust phosphoric acid retention ability. The nuclear magnetic resonance (NMR) hydrogen spectrum analysis results indicate the successful completion of the grafting reaction where N-alkylation reactions happen on both sides of the grafting agent 1,4-bis(chloromethyl)benzene. On one side, the reaction takes place with the hydrogen atoms on the imidazole groups of PBI, while on the other side, it reacts with the terminal amino group of PVP. The XPS results provide additional evidence from the perspective of the element. On synthesized PBI-g-PVP surfaces, there is an absence of chlorine (chlorine in grafting agent 1,4-bis(chloromethyl)benzene is substituted) element but a presence of sulfur element (sulfur element in terminal amino PVP appears in PBI), which demonstrates the occurrence of the grafting reaction and PVP is successfully grafted onto PBI. Prepare these modified membranes into MEA. It was found that during the fuel cell operation, all the grafted membranes showed substantial improvement in maximum current density and peak power density compared to unmodified one. For PBI-g-PVP 30, with a grafting degree of 22.4%, the peak power density reaches 1312 mW cm⁻², marking a 59.6% enhancement compared to the pristine PBI membrane. The improvement is caused by the improved PA binding ability of the membrane after grafting. The AST test result shows that the grafting membranes have better long-term durability and performance than unmodified membranes attributed to the presence of added PA binding sites, which can effectively prevent the PA leaching caused by proton migration. In conclusion, the test results indicate that grafting PVP onto PBI is a promising strategy which can effectively improve the fuel cell performance.

Keywords: fuel cell, grafting modification, PA doping ability, PVP

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Authors: E. Mosiniewicz-Szablewska, P. Suchocki, P. C. Morais

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Despite the significant progress in cancer treatment, there is a need to search for new therapeutic methods in order to minimize side effects. Chemotherapy, the main current method of treating cancer, is non-selective and has a number of limitations. Toxicity to healthy cells is undoubtedly the biggest problem limiting the use of many anticancer drugs. The problem of how to kill cancer without harming a patient can be solved by using organic selenium (IV) compounds. Organic selenium (IV) compounds are a new class of materials showing a strong anticancer activity. They are first organic compounds containing selenium at the +4 oxidation level and therefore they eliminate the multidrug-resistance for all tumor cell lines tested so far. These materials are capable of selectively killing cancer cells without damaging the healthy ones. They are obtained by the incorporation of selenous acid (H2SeO3) into molecules of fatty acids of sunflower oil and therefore, they are inexpensive to manufacture. Attaching these compounds to magnetic carriers enables their precise delivery directly to the tumor area and the simultaneous application of the magnetic hyperthermia, thus creating a huge opportunity to effectively get rid of the tumor without any side effects. Polylactic-co-glicolic acid (PLGA) nanocapsules loaded with maghemite (-Fe2O3) nanoparticles and organic selenium (IV) compounds are successfully prepared by nanoprecipitation method. In vitro antitumor activity of the nanocapsules were evidenced using murine melanoma (B16-F10), oral squamos carcinoma (OSCC) and murine (4T1) and human (MCF-7) breast lines. Further exposure of these cells to an alternating magnetic field increased the antitumor effect of nanocapsules. Moreover, the nanocapsules presented antitumor effect while not affecting normal cells. Magnetic properties of the nanocapsules were investigated by means of dc magnetization, ac susceptibility and electron spin resonance (ESR) measurements. The nanocapsules presented a typical superparamagnetic behavior around room temperature manifested itself by the split between zero field-cooled/field-cooled (ZFC/FC) magnetization curves and the absence of hysteresis on the field-dependent magnetization curve above the blocking temperature. Moreover, the blocking temperature decreased with increasing applied magnetic field. The superparamagnetic character of the nanocapsules was also confirmed by the occurrence of a maximum in temperature dependences of both real ′(T) and imaginary ′′ (T) components of the ac magnetic susceptibility, which shifted towards higher temperatures with increasing frequency. Additionally, upon decreasing the temperature the ESR signal shifted to lower fields and gradually broadened following closely the predictions for the ESR of superparamagnetoc nanoparticles. The observed superparamagnetic properties of nanocapsules enable their simple manipulation by means of magnetic field gradient, after introduction into the blood stream, which is a necessary condition for their use as magnetic drug carriers. The observed anticancer and superparamgnetic properties show that the magnetic nanocapsules loaded with organic selenium (IV) compounds should be considered as an effective material system for magnetic drug delivery and magnetohyperthermia inductor in antitumor therapy.

Keywords: cancer treatment, magnetic drug delivery system, nanomaterials, nanotechnology

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Authors: Jaden Lu, Olivia Lu

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Despite the remarkable advancement of solar cell technology, the challenge of optimizing total solar energy harvest efficiency persists, primarily due to significant heat loss. This excess heat not only diminishes solar panel output efficiency but also curtails its operational lifespan. A promising approach to address this issue is the conversion of surplus heat into electricity. In recent years, there is growing interest in the use of thermoelectric generators (TEG) as a potential solution. The integration of efficient TEG devices holds the promise of augmenting overall energy harvest efficiency while prolonging the longevity of solar panels. While certain research groups have proposed the integration of solar cells and TEG devices, a substantial gap between conceptualization and practical implementation remains, largely attributed to low thermal energy conversion efficiency of TEG devices. To bridge this gap and meet the requisites of practical application, a feasible strategy involves the incorporation of a substantial number of p-n junctions within a confined unit volume. However, the manufacturing of high-density TEG p-n junctions presents a formidable challenge. The prevalent solution often leads to large device sizes to accommodate enough p-n junctions, consequently complicating integration with solar cells. Recently, the adoption of 3D printing technology has emerged as a promising solution to address this challenge by fabricating high-density p-n arrays. Despite this, further developmental efforts are necessary. Presently, the primary focus is on the 3D printing of vertically layered TEG devices, wherein p-n junction density remains constrained by spatial limitations and the constraints of 3D printing techniques. This study proposes a novel device configuration featuring horizontally arrayed p-n junctions of Bi2Te3. The structural design of the device is subjected to simulation through the Finite Element Method (FEM) within COMSOL Multiphysics software. Various device configurations are simulated to identify optimal device structure. Based on the simulation results, a new TEG device is fabricated utilizing 3D Selective laser melting (SLM) printing technology. Fusion 360 facilitates the translation of the COMSOL device structure into a 3D print file. The horizontal design offers a unique advantage, enabling the fabrication of densely packed, three-dimensional p-n junction arrays. The fabrication process entails printing a singular row of horizontal p-n junctions using the 3D SLM printing technique in a single layer. Subsequently, successive rows of p-n junction arrays are printed within the same layer, interconnected by thermally conductive copper. This sequence is replicated across multiple layers, separated by thermal insulating glass. This integration created in a highly compact three-dimensional TEG device with high density p-n junctions. The fabricated TEG device is then attached to the bottom of the solar cell using thermal glue. The whole device is characterized, with output data closely matching with COMSOL simulation results. Future research endeavors will encompass the refinement of thermoelectric materials. This includes the advancement of high-resolution 3D printing techniques tailored to diverse thermoelectric materials, along with the optimization of material microstructures such as porosity and doping. The objective is to achieve an optimal and highly integrated PV-TEG device that can substantially increase the solar energy harvest efficiency.

Keywords: thermoelectric, finite element method, 3d print, energy conversion

Procedia PDF Downloads 35

Authors: Jaden Lu, Olivia Lu

Abstract:

Despite the remarkable advancement of solar cell technology, the challenge of optimizing total solar energy harvest efficiency persists, primarily due to significant heat loss. This excess heat not only diminishes solar panel output efficiency but also curtails its operational lifespan. A promising approach to address this issue is the conversion of surplus heat into electricity. In recent years, there is growing interest in the use of thermoelectric generators (TEG) as a potential solution. The integration of efficient TEG devices holds the promise of augmenting overall energy harvest efficiency while prolonging the longevity of solar panels. While certain research groups have proposed the integration of solar cells and TEG devices, a substantial gap between conceptualization and practical implementation remains, largely attributed to low thermal energy conversion efficiency of TEG devices. To bridge this gap and meet the requisites of practical application, a feasible strategy involves the incorporation of a substantial number of p-n junctions within a confined unit volume. However, the manufacturing of high-density TEG p-n junctions presents a formidable challenge. The prevalent solution often leads to large device sizes to accommodate enough p-n junctions, consequently complicating integration with solar cells. Recently, the adoption of 3D printing technology has emerged as a promising solution to address this challenge by fabricating high-density p-n arrays. Despite this, further developmental efforts are necessary. Presently, the primary focus is on the 3D printing of vertically layered TEG devices, wherein p-n junction density remains constrained by spatial limitations and the constraints of 3D printing techniques. This study proposes a novel device configuration featuring horizontally arrayed p-n junctions of Bi2Te3. The structural design of the device is subjected to simulation through the Finite Element Method (FEM) within COMSOL Multiphysics software. Various device configurations are simulated to identify optimal device structure. Based on the simulation results, a new TEG device is fabricated utilizing 3D Selective laser melting (SLM) printing technology. Fusion 360 facilitates the translation of the COMSOL device structure into a 3D print file. The horizontal design offers a unique advantage, enabling the fabrication of densely packed, three-dimensional p-n junction arrays. The fabrication process entails printing a singular row of horizontal p-n junctions using the 3D SLM printing technique in a single layer. Subsequently, successive rows of p-n junction arrays are printed within the same layer, interconnected by thermally conductive copper. This sequence is replicated across multiple layers, separated by thermal insulating glass. This integration created in a highly compact three-dimensional TEG device with high density p-n junctions. The fabricated TEG device is then attached to the bottom of the solar cell using thermal glue. The whole device is characterized, with output data closely matching with COMSOL simulation results. Future research endeavors will encompass the refinement of thermoelectric materials. This includes the advancement of high-resolution 3D printing techniques tailored to diverse thermoelectric materials, along with the optimization of material microstructures such as porosity and doping. The objective is to achieve an optimal and highly integrated PV-TEG device that can substantially increase the solar energy harvest efficiency.

Keywords: thermoelectric, finite element method, 3d print, energy conversion

Procedia PDF Downloads 35

Authors: Mazaher Yarmohamadi-Vasel, Ali Reza Modarresi-Alama, Sahar Shabzendedara

Abstract:

Purpose/Objectives: The first purpose was synthesize Poly(N-(sulfophenyl)aniline) nanoflowers (PSANFLs) and Poly(N-(sulfophenyl)aniline) nanofibers/titanium dioxide nanoparticles ((PSANFs/TiO2NPs) by a solid-state mechano-chemical reaction and template-free method and use them in hybrid solar cell. Also, our second aim was to increase the solubility and the processability of conjugated nanomaterials in water through polar functionalized materials. poly[N-(4-sulfophenyl)aniline] is easily soluble in water because of the presence of polar groups of sulfonic acid in the polymer chain. Materials/Methods: Iron (III) chloride hexahydrate (FeCl3∙6H2O) were bought from Merck Millipore Company. Titanium oxide nanoparticles (TiO2, <20 nm, anatase) and Sodium diphenylamine-4-sulfonate (99%) were bought from Sigma-Aldrich Company. Titanium dioxide nanoparticles paste (PST-20T) was prepared from Sharifsolar Co. Conductive glasses coated with indium tin oxide (ITO) were bought from Xinyan Technology Co (China). For the first time we used the solid-state mechano-chemical reaction and template-free method to synthesize Poly(N-(sulfophenyl)aniline) nanoflowers. Moreover, for the first time we used the same technique to synthesize nanocomposite of Poly(N-(sulfophenyl)aniline) nanofibers and titanium dioxide nanoparticles (PSANFs/TiO2NPs) also for the first time this nanocomposite was synthesized. Examining the results of electrochemical calculations energy gap obtained by CV curves and UV–vis spectra demonstrate that PSANFs/TiO2NPs nanocomposite is a p-n type material that can be used in photovoltaic cells. Doctor blade method was used to creat films for three kinds of hybrid solar cells in terms of different patterns like ITO│TiO2NPs│Semiconductor sample│Al. In the following, hybrid photovoltaic cells in bilayer and bulk heterojunction structures were fabricated as ITO│TiO2NPs│PSANFLs│Al and ITO│TiO2NPs│PSANFs /TiO2NPs│Al, respectively. Fourier-transform infrared spectra, field emission scanning electron microscopy (FE-SEM), ultraviolet-visible spectra, cyclic voltammetry (CV) and electrical conductivity were the analysis that used to characterize the synthesized samples. Results and Conclusions: FE-SEM images clearly demonstrate that the morphology of the synthesized samples are nanostructured (nanoflowers and nanofibers). Electrochemical calculations of band gap from CV curves demonstrated that the forbidden band gap of the PSANFLs and PSANFs/TiO2NPs nanocomposite are 2.95 and 2.23 eV, respectively. I–V characteristics of hybrid solar cells and their power conversion efficiency (PCE) under 100 mWcm−2 irradiation (AM 1.5 global conditions) were measured that The PCE of the samples were 0.30 and 0.62%, respectively. At the end, all the results of solar cell analysis were discussed. To sum up, PSANFLs and PSANFLs/TiO2NPs were successfully synthesized by an affordable and straightforward mechanochemical reaction in solid-state under the green condition. The solubility and processability of the synthesized compounds have been improved compared to the previous work. We successfully fabricated hybrid photovoltaic cells of synthesized semiconductor nanostructured polymers and TiO2NPs as different architectures. We believe that the synthesized compounds can open inventive pathways for the development of other Poly(N-(sulfophenyl)aniline based hybrid materials (nanocomposites) proper for preparing new generation solar cells.

Keywords: mechanochemical synthesis, PSANFLs, PSANFs/TiO2NPs, solar cell

Procedia PDF Downloads 40

Authors: Satam Alotibi, Osama A. Hussein, Aziz H. Al-Shaibani, Nawaf A. Al-Aqeel, Abdellah Kaiba, Fatehia S. Alhakami, Mohammed Alyami, Talal F. Qahtan

Abstract:

The demand for sustainable and efficient energy conversion using solar energy has grown rapidly in recent years. In this pursuit, solar-to-chemical conversion has emerged as a promising approach, with oxygen vacancies-rich tungsten trioxide (WO₃) playing a crucial role. This study presents a method for synthesizing oxygen vacancies-rich WO3, resulting in a significant enhancement of its photocatalytic activity, representing a significant step towards sustainable energy solutions. Experimental results underscore the importance of oxygen vacancies in modifying the properties of WO₃. These vacancies introduce additional energy states within the material, leading to a reduction in the bandgap, increased light absorption, and acting as electron traps, thereby reducing emissions. Our focus lies in developing oxygen vacancies-rich WO₃, which demonstrates unparalleled potential for improved photocatalytic applications. The effectiveness of oxygen vacancies-rich WO₃ in solar-to-chemical conversion was showcased through rigorous assessments of its photocatalytic degradation performance. Sunlight irradiation was employed to evaluate the material's effectiveness in degrading organic pollutants in wastewater. The results unequivocally demonstrate the superior photocatalytic performance of oxygen vacancies-rich WO₃ compared to conventional WO₃ nanomaterials, establishing its efficacy in sustainable and efficient energy conversion. Furthermore, the synthesized material is utilized to fabricate films, which are subsequently employed in immobilized WO₃ and oxygen vacancies-rich WO₃ reactors for water purification under natural sunlight irradiation. This application offers a sustainable and efficient solution for water treatment, harnessing solar energy for effective decontamination. In addition to investigating the photocatalytic capabilities, we extensively analyze the structural and chemical properties of the synthesized material. The synthesis process involves in situ thermal reduction of WO₃ nano-powder in a nitrogen environment, meticulously monitored using thermogravimetric analysis (TGA) to ensure precise control over the synthesis of oxygen vacancies-rich WO₃. Comprehensive characterization techniques such as UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), FTIR, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) provide deep insights into the material's optical properties, chemical composition, elemental states, structure, surface properties, and crystalline structure. This study represents a significant advancement in sustainable energy conversion through solar-to-chemical processes and water purification. By harnessing the unique properties of oxygen vacancies-rich WO₃, we not only enhance our understanding of energy conversion mechanisms but also pave the way for the development of highly efficient and environmentally friendly photocatalytic materials. The application of this material in water purification demonstrates its versatility and potential to address critical environmental challenges. These findings bring us closer to a sustainable energy future and cleaner water resources, laying a solid foundation for a more sustainable planet.

Keywords: sustainable energy conversion, solar-to-chemical conversion, oxygen vacancies-rich tungsten trioxide (WO₃), photocatalytic activity enhancement, water purification

Procedia PDF Downloads 35

Authors: E. Locatelli, I. Monaco, R. C. Martin, Y. Li, R. Pini, M. Chiariello, M. Comes Franchini

Abstract:

Despite the many advantages of application of nanomaterials in the field of nanomedicine, increasing concerns have been expressed on their potential adverse effects on human health. There is urgency for novel green strategies toward novel materials with enhanced biocompatibility using safe reagents. Photothermal ablation therapy, which exploits localized heat increase of a few degrees to kill cancer cells, has appeared recently as a non-invasive and highly efficient therapy against various cancer types; anyway new agents able to generate hyperthermia when irradiated are needed and must have precise biocompatibility in order to avoid damage to healthy tissues and prevent toxicity. Recently, there has been increasing interest in magnesium as a biomaterial: it is the fourth most abundant cation in the human body, and it is essential for human metabolism. However magnesium nanoparticles (Mg NPs) have had limited diffusion due to the high reduction potential of magnesium cations, which makes NPs synthesis challenging. Herein, we report the synthesis of Mg NPs and their surface functionalization for the obtainment of a stable and biocompatible nanomaterial suitable for photothermal ablation therapy against cancer. We synthesized the Mg crystals by reducing MgCl2 with metallic lithium and exploiting naphthalene as an electron carrier: the lithium–naphthalene complex acts as the real reducing agent. Firstly, the nanocrystal particles were coated with the ligand 12-ethoxy ester dodecanehydroxamic acid, and then entrapped into water-dispersible polymeric micelles (PMs) made of the FDA-approved PLGA-b-PEG-COOH copolymer using the oil-in-water emulsion technique. Lately, we developed a more straightforward methodology by introducing chitosan, a highly biocompatible natural product, at the beginning of the process, simultaneously using lithium–naphthalene complex, thus having a one-pot procedure for the formation and surface modification of MgNPs. The obtained MgNPs were purified and fully characterized, showing diameters in the range of 50-300 nm. Notably, when coated with chitosan the particles remained stable as dry powder for more than 10 months. We proved the possibility of generating a temperature rise of a few to several degrees once MgNPs were illuminated using a 810 nm diode laser operating in continuous wave mode: the temperature rise resulted significant (0-15 °C) and concentration dependent. We then investigated potential cytotoxicity of the MgNPs: we used HN13 epithelial cells, derived from a head and neck squamous cell carcinoma and the hepa1-6 cell line, derived from hepatocellular carcinoma and very low toxicity was observed for both nanosystems. Finally, in vivo photothermal therapy was performed on xenograft hepa1-6 tumor bearing mice: the animals were treated with MgNPs coated with chitosan and showed no sign of suffering after the injection. After 12 hours the tumor was exposed to near-infrared laser light. The results clearly showed an extensive damage to tumor tissue after only 2 minutes of laser irradiation at 3Wcm-1, while no damage was reported when the tumor was treated with the laser and saline alone in control group. Despite the lower photothermal efficiency of Mg with respect to Au NPs, we consider MgNPs a promising, safe and green candidate for future clinical translations.

Keywords: chitosan, magnesium nanoparticles, nanomedicine, photothermal therapy

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Authors: Marian Mihalik, Kornel Csach, Martin Kovalik, Matúš Mihalik, Martina Kubovčíková, Maria Zentková, Martin Vavra, Vladimír Girman, Jaroslav Briančin, Marija Perovic, Marija Boškovic, Magdalena Fitta, Robert Pelka

Abstract:

Current nanomaterials for use in biomedicine are based mainly on iron oxides and on present knowledge on magnetic nanostructures. Manganites can represent another material which can be used optionally. Manganites and their unique electronic properties have been extensively studied in the last decades not only due to fundamental interest but to possible applications of colossal magnetoresistance, magnetocaloric effect, and ferroelectric properties. It was found that the oxygen-reduction reaction on perovskite oxide is intimately connected with metal ion e.g., orbital occupation. The effect of oxygen deviation from the stoichiometric composition on crystal structure was studied very carefully by many authors on LaMnO₃. Depending on oxygen content, the crystal structure changes from orthorhombic one to rhombohedric for oxygen content 3.1. In the case of hole-doped manganites, the change from the orthorhombic crystal structure, which is typical for La1-xCaxMnO3 based manganites, to the rhombohedric crystal structure (La1-xMxMnO₃ where M = K, Ag, and Sr based materials) results in an enormous increase of the Curie temperature. In our paper, we study the effect of oxygen content on crystal structure, thermal, and magnetic properties (including magnetocaloric effect) of La1-xAgxMnO₃nano particle system. The content of oxygen in samples was tuned by heat treatment in different thermal regimes and in various environment (air, oxygen, argon). Water nanosuspensions based on La0.80Ag0.15MnO₃ magnetic particles with the Curie temperature of about 43oC were prepared by two different approaches. First, by using a laboratory circulation mill for milling of powder in the presence of sodium dodecyl sulphate (SDS) and subsequent centrifugation. Second nanosuspension was prepared using an agate bowl, etching in citric acid and HNO3, ultrasound homogeniser, centrifugation, and dextran 40 kDA or 15 kDA as surfactant. Electrostatic stabilisation obtained by the first approach did not offer long term kinetic and aggregation colloidal stability and was unable to compensate for attractive forces between particles under a magnetic field. By the second approach, we prepared suspension oversaturated by dextran 40 kDA for steric stabilisation, with evidence of the presence of superparamagnetic behaviour. Low concentration of nanoparticles and not ideal coverage of nanoparticles impacting the stability of ferrofluids was the disadvantage of this approach. Strong steric stabilisation was observable at alcaic conditions under pH = ~10. Application of dextran 15 kDA leads to relatively stable ferrofluid with pH around physiological conditions, but desegregation of powder by HNO₃ was not effective enough, and the average size of fragments was to large of about 150 nm, and we did not see any signature of superparamagnetic behaviour. The prepared ferrofluids were characterised by scanning and transition microscope method, thermogravimetry, magnetization, and AC susceptibility measurements. Specific Absorption Rate measurements were undertaken on powder as well on ferrofluids in order to estimate the potential application of La₀.₈₀Ag₀.₁₅MnO₃ magnetic particles based ferrofluid for hyperthermia. Our complex study contains an investigation of biocompatibility and potential biohazard of this material.

Keywords: manganites, magnetic nanoparticles, oxygen content, magnetic phase transition, magnetocaloric effect, ferrofluid, hyperthermia

Procedia PDF Downloads 63

Authors: Dina Ibrahim Abouelamaiem, Ana Jorge Sobrido, Magdalena Titirici, Paul R. Shearing, Daniel J. L. Brett

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Global warming and scarcity of fossil fuels have had a radical impact on the world economy and ecosystem. The urgent need for alternative energy sources has hence elicited an extensive research for exploiting efficient and sustainable means of energy conversion and storage. Among various electrochemical systems, supercapacitors attracted significant attention in the last decade due to their high power supply, long cycle life compared to batteries and simple mechanism. Recently, the performance of these devices has drastically improved, as tuning of nanomaterials provided efficient charge and storage mechanisms. Carbon materials, in various forms, are believed to pioneer the next generation of supercapacitors due to their attractive properties that include high electronic conductivities, high surface areas and easy processing and functionalization. Cellulose has eco-friendly attributes that are feasible to replace man-made fibers. The carbonization of cellulose yields carbons, including activated carbon and graphite fibers. Activated carbons successively are the most exploited candidates for supercapacitor electrode materials that can be complemented with pseudocapacitive materials to achieve high energy and power densities. In this work, the optimum functionalization conditions of cellulose have been investigated for supercapacitor electrode materials. The precursor was treated with potassium hydroxide (KOH) at different KOH/cellulose ratios prior to the carbonization process in an inert nitrogen atmosphere at 850 °C. The chalky products were washed, dried and characterized with different techniques including transmission electron microscopy (TEM), x-ray tomography and nitrogen adsorption-desorption isotherms. The morphological characteristics and their effect on the electrochemical performances were investigated in two and three-electrode systems. The KOH/cellulose ratios of 0.5:1 and 1:1 exhibited the highest performances with their unique hierarchal porous network structure, high surface areas and low cell resistances. Both samples acquired the best results in three-electrode systems and coin cells with specific gravimetric capacitances as high as 187 F g-1 and 20 F g-1 at a current density of 1 A g-1 and retention rates of 72% and 70%, respectively. This is attributed to the morphology of the samples that constituted of a well-balanced micro-, meso- and macro-porosity network structure. This study reveals that the electrochemical performance doesn’t solely depend on high surface areas but also an optimum pore size distribution, specifically at low current densities. The micro- and meso-pore contribution to the final pore structure was found to dominate at low KOH loadings, reaching ‘equilibrium’ with macropores at the optimum KOH loading, after which macropores dictate the porous network. The wide range of pore sizes is detrimental for the mobility and penetration of electrolyte ions in the porous structures. These findings highlight the influence of various morphological factors on the double-layer capacitances and high performance rates. In addition, they open a platform for the investigation of the optimized conditions for double-layer capacitance that can be coupled with pseudocapacitive materials to yield higher energy densities and capacities.

Keywords: carbon, electrochemical performance, electrodes, KOH/cellulose optimized ratio, morphology, supercapacitor

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Authors: Laura Norfolk, Georgina Zimbitas, Jan Sefcik, Sarah Staniland

Abstract:

Magnetite nanoparticles (MNP) have been an area of increasing research interest due to their extensive applications in industry, such as in carbon capture, water purification, and crucially, the biomedical industry. The use of MNP in the biomedical industry is rising, with studies on their effect as Magnetic resonance imaging contrast agents, drug delivery systems, and as hyperthermic cancer treatments becoming prevalent in the nanomaterial research community. Particles used for biomedical purposes must meet stringent criteria; the particles must have consistent shape and size between particles. Variation between particle morphology can drastically alter the effective surface area of the material, making it difficult to correctly dose particles that are not homogeneous. Particles of defined shape such as octahedral and cubic have been shown to outperform irregular shaped particles in some applications, leading to the need to synthesize particles of defined shape. In nature, highly homogeneous MNP are found within magnetotactic bacteria, a unique bacteria capable of producing magnetite nanoparticles internally under ambient conditions. Biomineralisation proteins control the properties of the MNPs, enhancing their homogeneity. One of these proteins, Mms6, has been successfully isolated and used in vitro as an additive in room-temperature co-precipitation reactions (RTCP) to produce particles of defined mono-dispersed size & morphology. When considering future industrial scale-up it is crucial to consider the costs and feasibility of an additive, as an additive that is not readily available or easily synthesized at a competitive price will not be sustainable. As such, additives selected for this research are inspired by the functional groups of biomineralisation proteins, but cost-effective, environmentally friendly, and compatible with scale-up. Diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA) have been successfully used in RTCP to modulate the properties of particles synthesized, leading to the formation of octahedral nanoparticles with no use of organic solvents, heating, or toxic precursors. By extending this principle to a fluidic system, ongoing research will reveal whether the amine additives can also exert morphological control in an environment which is suited toward higher particle yield. Two fluidic systems have been employed; a peristaltic turbulent flow mixing system suitable for the rapid production of MNP, and a macrofluidic system for the synthesis of tailored nanomaterials under a laminar flow regime. The presence of the amine additives in the turbulent flow system in initial results appears to offer similar morphological control as observed under RTCP conditions, with higher proportions of octahedral particles formed. This is a proof of concept which may pave the way to green synthesis of tailored MNP on an industrial scale. Mms6 and amine additives have been used in the macrofluidic system, with Mms6 allowing magnetite to be synthesized at unfavourable ferric ratios, but no longer influencing particle size. This suggests this synthetic technique while still benefiting from the addition of additives, may not allow additives to fully influence the particles formed due to the faster timescale of reaction. The amine additives have been tested at various concentrations, the results of which will be discussed in this paper.

Keywords: bioinspired, green synthesis, fluidic, magnetite, morphological control, scale-up

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Authors: Adewale Tolulope Irewale, Elias Emeka Elemike, Christian O. Dimkpa, Emeka Emmanuel Oguzie

Abstract:

As the global population steadily approaches the 10billion mark, the world is currently faced with two major challenges among others – accessing sustainable and clean energy, and food security. Accessing cleaner and sustainable energy sources to drive global economy and technological advancement, and feeding the teeming human population require sustainable, innovative, and smart solutions. To solve the food production problem, producers have relied on fertilizers as a way of improving crop productivity. Commercial inorganic fertilizers, which is employed to boost agricultural food production, however, pose significant ecological sustainability and economic problems including soil and water pollution, reduced input efficiency, development of highly resistant weeds, micronutrient deficiency, soil degradation, and increased soil toxicity. These ecological and sustainability concerns have raised uncertainties about the continued effectiveness of conventional fertilizers. With the application of nanotechnology, plant biomass upcycling offers several advantages in greener energy production and sustainable agriculture through reduction of environmental pollution, increasing soil microbial activity, recycling carbon thereby reducing GHG emission, and so forth. This innovative technology has the potential for a circular economy and creating a sustainable agricultural practice. Nanomaterials have the potential to greatly enhance the quality and nutrient composition of organic biomass which in turn, allows for the conversion of biomass into nanofertilizers that are potentially more efficient. Water hyacinth plant harvested from an inland water at Warri, Delta State Nigeria were air-dried and milled into powder form. The dry biomass were used to prepare biochar at a pre-determined temperature in an oxygen deficient atmosphere. Physicochemical analysis of the resulting biochar was carried out to determine its porosity and general morphology using the Scanning Transmission Electron Microscopy (STEM). The functional groups (-COOH, -OH, -NH2, -CN, -C=O) were assessed using the Fourier Transform InfraRed Spectroscopy (FTIR) while the heavy metals (Cr, Cu, Fe, Pb, Mg, Mn) were analyzed using Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES). Impregnation of the biochar with nanonutrients were achieved under varied conditions of pH, temperature, nanonutrient concentrations and resident time to achieve optimum adsorption. Adsorption and desorption studies were carried out on the resulting nanofertilizer to determine kinetics for the potential nutrients’ bio-availability to plants when used as green fertilizers. Water hyacinth (Eichhornia crassipes) which is an aggressively invasive aquatic plant known for its rapid growth and profusion is being examined in this research to harness its biomass as a sustainable feedstock to formulate functionalized nano-biochar fertilizers, offering various benefits including water hyacinth biomass upcycling, improved nutrient delivery to crops and aquatic ecosystem remediation. Altogether, this work aims to create output values in the three dimensions of environmental, economic, and social benefits.

Keywords: biochar-based nanofertilizers, eichhornia crassipes, greener agriculture, sustainable ecosystem, water hyacinth

Procedia PDF Downloads 26

Authors: Jocelyn Doucet, Jean-Philippe Laviolette, Ali Eslami

Abstract:

The end-of-life management and recycling of polymer wastes remains a key environment issue in on-going efforts to increase resource efficiency and attaining GHG emission reduction targets. Half of all the plastics ever produced were made in the last 13 years, and only about 16% of that plastic waste is collected for recycling, while 25% is incinerated, 40% is landfilled, and 19% is unmanaged and leaks in the environment and waterways. In addition to the plastic collection issue, the UN recently published a report on chemicals in plastics, which adds another layer of challenge when integrating recycled content containing toxic products into new products. To tackle these important issues, innovative solutions are required. Chemical recycling of plastics provides new complementary alternatives to the current recycled plastic market by converting waste material into a high value chemical commodity that can be reintegrated in a variety of applications, making the total market size of the output – virgin-like, high value products - larger than the market size of the input – plastic waste. Access to high-quality feedstock also remains a major obstacle, primarily due to material contamination issues. Pyrowave approaches this challenge with its innovative nano-recycling technology, which purifies polymers at the molecular level, removing undesirable contaminants and restoring the resin to its virgin state without having to depolymerise it. This breakthrough approach expands the range of plastics that can be effectively recycled, including mixed plastics with various contaminants such as lead, inorganic pigments, and flame retardants. The technology allows yields below 100ppm, and purity can be adjusted to an infinitesimal level depending on the customer's specifications. The separation of the polymer and contaminants in Pyrowave's nano-recycling process offers the unique ability to customize the solution on targeted additives and contaminants to be removed based on the difference in molecular size. This precise control enables the attainment of a final polymer purity equivalent to virgin resin. The patented process involves dissolving the contaminated material using a specially formulated solvent, purifying the mixture at the molecular level, and subsequently extracting the solvent to yield a purified polymer resin that can directly be reintegrated in new products without further treatment. Notably, this technology offers simplicity, effectiveness, and flexibility while minimizing environmental impact and preserving valuable resources in the manufacturing circuit. Pyrowave has successfully applied this nano-recycling technology to decontaminate polymers and supply purified, high-quality recycled plastics to critical industries, including food-contact compliance. The technology is low-carbon, electrified, and provides 100% traceable resins with properties identical to those of virgin resins. Additionally, the issue of low recycling rates and the limited market for traditionally hard-to-recycle plastic waste has fueled the need for new complementary alternatives. Chemical recycling, such as Pyrowave's microwave depolymerization, presents a sustainable and efficient solution by converting plastic waste into high-value commodities. By employing microwave catalytic depolymerization, Pyrowave enables a truly circular economy of plastics, particularly in treating polystyrene waste to produce virgin-like styrene monomers. This revolutionary approach boasts low energy consumption, high yields, and a reduced carbon footprint. Pyrowave offers a portfolio of sustainable, low-carbon, electric solutions to give plastic waste a second life and paves the way to the new circular economy of plastics. Here, particularly for polystyrene, we show that styrene monomer yields from Pyrowave’s polystyrene microwave depolymerization reactor is 2,2 to 1,5 times higher than that of the thermal conventional pyrolysis. In addition, we provide a detailed understanding of the microwave assisted depolymerization via analyzing the effects of microwave power, pyrolysis time, microwave receptor and temperature on the styrene product yields. Furthermore, we investigate life cycle environmental impact assessment of microwave assisted pyrolysis of polystyrene in commercial-scale production. Finally, it is worth pointing out that Pyrowave is able to treat several tons of polystyrene to produce virgin styrene monomers and manage waste/contaminated polymeric materials as well in a truly circular economy.

Keywords: nanorecycling, nanomaterials, plastic recycling, depolymerization

Procedia PDF Downloads 38

Authors: Ziyad S. Haidar

Abstract:

Millions of teeth are removed annually, and dental extraction is one of the most commonly performed surgical procedures globally. Whether due to caries, periodontal disease or trauma, exodontia and the ensuing wound healing and bone remodeling processes of the resultant socket (hole in the jaw bone) usually result in serious deformities of the residual alveolar osseous ridge and surrounding soft tissues (reduced height/width). Such voluminous changes render the placement of a proper conventional bridge, denture or even an implant-supported prosthesis extremely challenging. Further, most extractions continue to be performed with no regard for preventing the onset of alveolar osteitis (also known as dry socket, a painful and difficult-to-treat/-manage condition post-exodontia). Hence, such serious resorptive morphological changes often result in significant facial deformities and a negative impact on the overall Quality of Life (QoL) of patients (and oral health-related QoL), alarming, particularly for the geriatric with compromised healing and in light of the thriving longevity statistics. Opportunity: Despite advances in tissue/wound grafting, serious limitations continue to exist, including efficacy and clinical outcome predictability, cost, treatment time, expertise and risk of immune reactions. For cases of dry sockets, specifically, the commercially-available and often-prescribed home remedies are highly lacking. Indeed, most are not recommended for use anymore. Alveogyl is a fine example. Hence, there is a great market demand and need for alternative solutions. Solution: Herein, SockGEL/PLUG (patent pending), an all-natural, drug-free and injectable stimuli-responsive hydrogel, was designed, formulated, characterized and evaluated as an osteogenic, angiogenic, anti-microbial and pain-soothing suture-free intra-alveolar dressing, safe and efficacious for use in several oro-dental and cranio-maxillo-facial interventional applications; for example: in fresh dental extraction sockets, immediately post-exodontia. It is composed of FDA-approved, biocompatible and biodegradable polymers, self-assembled electro-statically to formulate a scaffolding matrix to (a) prevent the onset of alveolar osteitis via securing the fibrin-clot in situ and protecting/sealing the socket from contamination/infection; and (b) endogenously promote/accelerate wound healing and bone remodeling to preserve the volume of the alveolus. Findings: The intrinsic properties of the SockGEL/PLUG hydrogel were evaluated physico-chemico-mechanically for safety (cell viability), viscosity, rheology, bio-distribution and essentially, capacity to induce wound healing and osteogenesis (small defect, in vivo) without any signaling cues from exogenous cells, growth factors or drugs. The performed animal model of cranial critical-sized and non-vascularized bone defects shall provide vitally critical insights into the role and mechanism of the employed natural bio-polymer blend and gel product in endogenous reparative regeneration of soft tissues and bone morphogenesis. Alongside, the fine-tuning of our modified formulation method will further tackle appropriateness, reproducibility, scalability, ease and speed in producing stable, biodegradable and sterilizable stimuli (thermo-sensitive and photo-responsive) matrices (3-dimensional interpenetrating yet porous polymeric network) suitable for an intra-socket application, and beyond. Conclusions and Perspective: Findings are anticipated to provide sufficient evidence to translate into pilot clinical trials and validate the bionanomaterial before engaging the market for feasibility, acceptance and cost-effectiveness studies. The SockGEL/PLUG platform is patent pending: SockGEL is a bio-inspired drug-free hydrogel; SockPLUG is a drug-loaded hydrogel designed for complex indications.

Keywords: hydrogel, injectable, dentistry, craniomaxillofacial complex, bioinspired, nanobiotechnology, biopolymer, sol-gel, stimuli-responsive, matrix, tissue engineering, regenerative medicine

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