Search results for: zirconium monosulfide

Authors: Khaled Alshamari

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Synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, HNMR, C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 ◦C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model, with a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ∆S (−0.03 kJ/mol), ∆H (−12.22 kJ/mol) and ∆G were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴+ (28.82), Fe³+ (10.64), Ti⁴+ (28.82), V⁵+ (86.46) and U⁶+ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.

Keywords: zirconium extraction, partially phosphorylated polyvinyl phosphate (PPVP), acidic medium, zircon

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Authors: Amir Raeisdana, Davood Sohrabi, Mojtaba Nohekhan, Ameneh Kargarian, Maryam Ghapanvari, Alireza Aslezaeem

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Improvement of zirconium properties by chromium coating and nitrogen implantation is ideal to protect the nuclear fuel rods against corrosion and secondary hydrogenation. Metallic chromium (Cr) has attracted attention as a potential coating material on zirconium alloys, to limit external cladding corrosion. In this research, high energy plasma focus device was used to coat the chromium and implant the nitrogen ions in the zirconium substrate. This device emits high-energy nitrogen ions of 10 keV-1 MeV and with a flux of 10^16 ions/cm^2 in each shot toward the target so it is attractive for implantation on the substrate materials at the room temperature. Six zirconium samples in 2cm×2cm dimensions with 1mm thickness were located at a distance of 20cm from the place where the pinch is formed. The experiments are carried out in 0.5 mbar of the nitrogen gas pressure and 15 kV of the charging voltage. Pure Cr disc was installed on the anode head for sputtering of the chromium and deposition on zirconium substrate. When the pinch plasma column decays due to various instabilities, intense and high-energy N2 ions are accelerated towards the zirconium substrate also sputtered Cr is deposited on the zirconium substrate. XRD and XRF analysis were used to study the structural properties of the samples. XRF analysis indicates 77.1% of Zr and 11.1% of Cr in the surface of the sample. XRD spectra shows the formation of ZrN, CrN and CrZr composites after nitrogen implantation and chromium coating. XRD spectra shows the chromium peak height equal to 152.80 a.u. for the major sample (θ=0֯) and 92.99 a.u. for the minor sample (θ=6֯), so implantation and coating along the main axis of the device is significantly more than other directions.

Keywords: ZrN and CrN and CrZr composites, angular distribution for Cr deposition rate, zirconium corrosion resistance, nuclear fuel rods, plasma focus device

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Authors: M. Ramachandra, G. Dilip Maruthi, R. Rashmi

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This paper aims to study the corrosion property of aluminum matrix nanocomposite of an aluminum alloy (Al-6061) reinforced with zirconium dioxide (ZrO₂) particles. The zirconium dioxide particles are synthesized by solution combustion method. The nanocomposite materials are prepared by mechanical stir casting method, varying the percentage of n-ZrO₂ (2.5%, 5% and 7.5% by weight). The corrosion behavior of base metal (Al-6061) and Al/ZrO₂ nanocomposite in seawater (3.5% NaCl solution) is measured using the potential control method. The corrosion rate is evaluated by Tafel extrapolation technique. The corrosion potential increases with the increase in wt.% of n-ZrO₂ in the nanocomposite which means the decrease in corrosion rate. It is found that on addition of n-ZrO2 particles to the aluminum matrix, the corrosion rate has decreased compared to the base metal.

Keywords: Al6061 alloy, corrosion, solution, stir casting, combustion, potentiostat, zirconium dioxide

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Authors: Makhlouf Sandy, Adem Ziad, Taher Fadia, Magnier Sylvie

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The electronic structure of 90ZrS has been investigated using Ab-initio methods based on Complete Active Space Self Consistent Field and Multi-reference Configuration Interaction (CASSCF/MRCI). The number of predicted states has been extended to 14 singlet and 12 triplet lowest-lying states situated below 36000cm-1. The equilibrium energies of these 26 lowest-lying electronic states have been calculated in the 2S+1Λ(±) representation. The potential energy curves have been plotted in function of the inter-nuclear distances in a range of 1.5 to 4.5Å. Spectroscopic constants, permanent electric dipole moments and transition dipole moments between the different electronic states have also been determined. A discrepancy error of utmost 5% for the majority of values shows a good agreement with available experimental data. The ground state is found to be of symmetry X1Σ+ with an equilibrium inter-nuclear distance Re= 2.16Å. However, the (1)3Δ is the closest state to X1Σ+ and is situated at 514 cm-1. To the best of our knowledge, this is the first time that the spin-orbit coupling has been investigated for all the predicted states of ZrS. 52 electronic components in the Ω(±) representation have been predicted. The energies of these components, the spectroscopic constants ωe, ωeχe, βe and the equilibrium inter-nuclear distances have been also obtained. The percentage composition of the Ω state wave-functions in terms of S-Λ states was calculated to identify their corresponding main parents. These (SOC) calculations have determined the shift between (1)3Δ1 and X1Σ+ states and confirmed the ground state type being 1Σ+.

Keywords: CASSCF/MRCI, electronic structure, spin-orbit effect, zirconium monosulfide

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Authors: G. Çelik Gül, F. Kurtuluş

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Rare earths containing complex metal oxides have drawn much attention due to physical, chemical and optical properties which make them feasible in so many areas such as non-linear optical materials and ion exchanger. We have researched a systematic study to obtain rare earth containing zirconium molybdate compound, characterization, investigation of crystal system and calculation of unit cell parameters.  After a successful synthesis of Nd₂Zr₃(MoO₄)₉ which is a member of rare earth metal containing complex oxides family, X-ray diffraction (XRD), High Score Plus/Rietveld refinement analysis, and Fourier Transform Infrared Spectroscopy (FTIR) were completed to determine the crystal structure. Morphological properties and elemental composition were determined by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. Thermal properties were observed via Thermogravimetric-differential thermal analysis (TG/DTA).

Keywords: Nd₂Zr₃(MoO₄)₉, powder x-ray diffraction, solid state synthesis, zirconium molybdates

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Authors: Roman J. Jedrzejczyk, Damian K. Chlebda, Anna Dziedzicka, Rafal Wazny, Agnieszka Domka, Maciej Sitarz, Przemyslaw J. Jodlowski

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The aim of this study was to obtain antimicrobial material based on thin zirconium dioxide coatings on structured reactors doped with metal nanoparticles using the sonochemical sol-gel method. As a result, dense, uniform zirconium dioxide films were obtained on the kanthal sheets which can be used as support materials in antimicrobial converters with sophisticated shapes. The material was characterised by physicochemical methods, such as AFM, SEM, EDX, XRF, XRD, XPS and in situ Raman and DRIFT spectroscopy. In terms of antimicrobial activity, the material was tested by ATP/AMP method using model microbes isolated from the real systems. The results show that the material can be potentially used in the market as a good candidate for active package and as active bulkheads of climatic systems. The mechanical tests showed that the developed method is an efficient way to obtain durable converters with high antimicrobial activity against fungi and bacteria.

Keywords: antimicrobial properties, kanthal steel, nanocomposite, zirconium oxide

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Authors: Salem El Ashoor, Fathia M. El-Meheishi, Ibtisam M. Diab

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Zirconium diammin and triammin complexes can be possess biological activities, these complexes were synthesized via the reaction equimolar quantity of (1:10-phenanthroline){NC3H3(C6H2)NC3H3} (L1) or 4-4-amino phenazone {ONC6H5(NH)CH(NH2} (L2) or diphenyl carbizon {HNNCO(NH)2(C6H5)} (L3) with Zirconium Salt {ZrOCl2} in ratio (1:1) to form complexes [{NC3H3(C6H2)NC3H3}ZrOCl2}] [ZrOCl2L1], [{(O2NC6H4(NH)(NH2)}ZrOCl2] [ZrOCl2L2] and [{HNNCO(NH)2(C6H5)ZrOCl2}] [ZrOCl2L3] respectively. The characterization of these complexes were follow by using Fourier Transform Infrared (FT-IR) and UV-Visible spectroscopy. Also a variable temperature study of these complexes has been followed by using UV-Visible spectroscopy to follow electronic transform behaviors under temperature control also DFT study calculation was follow these complexes via the information from FT-IR and UV-Visible spectroscopy. A coordination number of these complexes of types five and six of the geometry can be suggested. These complexes were found to shown deferent inhibition to the growth of bacterial strains of Bacillus spp & Klebsiella spp & E.coli & proteus spp & pseudomona spp) while all complexes were in deferent's concentration (0.001, 0.2 and 1M) and the result as evidenced from the presence. For better understanding these complexes were examined by using Density functional theory (DFT) calculation.

Keywords: (1:10-phenanthroline) (L1), 4-4-amino phenazone (L2), diphenyl carbizon (L3), DFT study, antibacterial

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Authors: Bharat Kumar, Deepak Kumar, Vijay Chaudhry

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Zirconium alloys exhibit low neutron absorption cross-section and excellent mechanical properties. Due to these unique characteristics, these materials are widely used in designing core components of pressurized heavy water reactors (PHWRs). Another material that is widely used in the design of reactor core is stainless steel. Under operating conditions of the reactor, there are possibilities for mechanical and tribological interaction between the components made of zirconium alloy (Zr-2.5 Nb) and stainless steel (SS-410). This may result in wear of the material. To study the tribological characteristics of Zr-2.5 Nb and SS-410, low amplitude reciprocating wear tests are conducted at room temperature and at high temperatures (260 degrees Celsius). The tests are conducted at frequencies ranging from 5 Hz to 25 Hz. The displacement amplitude is varied from 200 µm to 600 µm. The responses are recorded, analyzed and correlated with damage observed using scanning electron microscopy (SEM) and an optical profilometer. Energy dispersive spectroscopy (EDS) is used to study the damage mechanism prevailing at the contact interface. A higher coefficient of friction (COF) is observed at higher temperatures as compared to the one at room temperature. Tests carried out at high temperature reveals adhesive wear as the dominant mechanism resulting in significant material transfer.

Keywords: PHWRs, Zr-2.5Nb, SS-410, wear

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Authors: Bharat Kumar, Deepak Kumar, Vijay Chaudhry

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Zirconium alloys are used as core components of nuclear reactors due to their high wear resistance, good corrosion properties, and good mechanical stability at high temperatures. Water flows inside the pressure tube through fuel claddings, which produces vibration of these core components and results in the wear of some components. Some components are subjected to the environment of coolant water containing LiOH which results in the corrosion of these components. The present work simulates some of these conditions to determine the failure mechanisms under these conditions and the effect of various parameters on them. Friction and wear experiments were performed varying the surrounding environment (room temperature, high temperature, and water submerged), duration, frequency, and displacement amplitude. Electrochemical corrosion experiments were performed by varying the concentration of LiOH in water. The worn and corroded surfaces were analyzed using scanning electron microscopy (SEM) to analyze the wear and corrosion mechanism and energy dispersive x-ray spectroscopy (EDS) and Raman spectroscopy to analyze the tribo-oxide layer formed during the wear and oxide layer formed during the corrosion. Wear increases with frequency and amplitude, and corrosion increases with LiOH concentration in water.

Keywords: zirconium alloys, wear, oxide layer, corrosion, EIS, linear polarization

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Authors: Rasha Al-Saedi, Anthony Meijer

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The progress of new porous materials has increased rapidly over the past decade for use in applications such as catalysis, gas storage and removal of environmentally unfriendly species due to their high surface area and high thermal stability. In this work, a theoretical study of the zirconium-based metal organic framework (MOFs) were examined in order to determine their potential for gas adsorption of various guest molecules: CO2, N2, CH4 and H2. The zirconium cluster consists of an inner Zr6O4(OH)4 core in which the triangular faces of the Zr6- octahedron are alternatively capped by O and OH groups which bound to nine formate groups and three benzoate groups linkers. General formula is [Zr(μ-O)4(μ-OH)4(HCOO)9((phyO2C)3X))] where X= CH2OH, CH2NH2, CH2CONH2, n(NH2); (n = 1-3). Three types of adsorption sites on the Zr metal center have been studied, named according to capped chemical groups as the ‘−O site’; the H of (μ-OH) site removed and added to (μ-O) site, ‘–OH site’; (μ-OH) site removed, the ‘void site’ where H2O molecule removed; (μ-OH) from one site and H from other (μ-OH) site, in addition to no defect versions. A series of investigations have been performed aiming to address this important issue. First, density functional theory DFT-B3LYP method with 6-311G(d,p) basis set was employed using Gaussian 09 package in order to evaluate the gas adsorption performance of missing-linker defects in zirconium cluster. Next, study the gas adsorption behaviour on different functionalised zirconium clusters. Those functional groups as mentioned above include: amines, alcohol, amide, in comparison with non-substitution clusters. Then, dispersion-corrected density functional theory (DFT-D) calculations were performed to further understand the enhanced gas binding on zirconium clusters. Finally, study the water effect on CO2 and N2 adsorption. The small functionalized Zr clusters were found to result in good CO2 adsorption over N2, CH4, and H2 due to the quadrupole moment of CO2 while N2, CH4 and H2 weakly polar or non-polar. The adsorption efficiency was determined using the dispersion method where the adsorption binding improved as most of the interactions, for example, van der Waals interactions are missing with the conventional DFT method. The calculated gas binding strengths on the no defect site are higher than those on the −O site, −OH site and the void site, this difference is especially notable for CO2. It has been stated that the enhanced affinity of CO2 of no defect versions is most likely due to the electrostatic interactions between the negatively charged O of CO2 and the positively charged H of (μ-OH) metal site. The uptake of the gas molecule does not enhance in presence of water as the latter binds to Zr clusters more strongly than gas species which attributed to the competition on adsorption sites.

Keywords: density functional theory, gas adsorption, metal- organic frameworks, molecular simulation, porous materials, theoretical chemistry

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Authors: Sanjida Akter, Ambali Alade Odebowale, Andrey E. Miroshnichenko, Haroldo T. Hattori

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Photodetectors (PDs) play a pivotal role in optoelectronics and optical devices, serving as fundamental components that convert light signals into electrical signals. As the field progresses, the integration of advanced materials with unique optical properties has become a focal point, paving the way for the innovation of novel PDs. This study delves into the exploration of a cutting-edge photodetector designed for deep and near ultraviolet (UV) applications. The photodetector is constructed with a composite of Zirconium Boride (ZrB2) and Chromium (Cr) alloy, deposited onto a 6H nitrogen-doped silicon carbide substrate. The determination of the optimal alloy thickness is achieved through Finite-Difference Time-Domain (FDTD) simulation, and the synthesis of the alloy is accomplished using radio frequency (RF) sputtering. Remarkably, the resulting photodetector exhibits an exceptional responsivity of 3.5 A/W under an applied voltage of -2 V, at wavelengths of 405 nm and 280 nm. This heterostructure not only exemplifies high performance but also provides a versatile platform for the development of near UV photodetectors capable of operating effectively in challenging conditions, such as environments characterized by high power and elevated temperatures. This study contributes to the expanding landscape of photodetector technology, offering a promising avenue for the advancement of optoelectronic devices in demanding applications.

Keywords: responsivity, silicon carbide, ultraviolet photodetector, zirconium boride

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Authors: Haesook Kim, Ha Na Ra, Mansu Kim, Hyun Gi Kim, Sung Soo Kim

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Epoxy-ZrP (α-zirconium phosphate) nanocomposites were coated on inorganic barrier layer such as sputtering and atomic layer deposition (ALD) to improve the barrier properties and protect the layer. ZrP nanoplatelets were synthesized using a reflux method and exfoliated in the polymer matrix. The barrier properties of coating layer were characterized by measuring water vapor transmission rate (WVTR). The WVTR dramatically decreased after epoxy-ZrP nanocomposite coating, while maintaining the optical properties. It was also investigated the effect of epoxy-ZrP coating on inorganic layer after bending and reliability test. The optimal structure composed of inorganic and epoxy-ZrP nanocomposite layers was used in organic light emitting diodes (OLED) encapsulation.

Keywords: α-zirconium phosphate, barrier properties, epoxy nanocomposites, OLED encapsulation

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Authors: Emrah Yaliniz, Ali Kalkanli

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ZE41A magnesium alloy has been extensively used in aerospace industry, especially for use in rotorcraft transmission casings. Due to the improved mechanical properties, the latest generation of magnesium casting alloy EV31A-T6 (Elektron 21® specified in AMS 4429) is seen as a potential replacement for ZE41A in terms of strength. Therefore, the necessity of enhancement has been arisen for ZE41A in order to avoid fully replacement. The main element affecting the strength of ZE41A is Zirconium (Zr), which acts as a grain refiner. The specified range of Zr element for ZE41A alloy is between 0.4 wt % and 1.0 wt % (unless otherwise stated by weight percentage after this point) as stated in AMS 4439. This paper investigates the effects of Zr amount on tensile and metallurgical properties of ZE41A magnesium alloy. The Zr alloying amount for the research has been chosen as 0.5 % and 1 %, which are standard amounts in a commercial alloy (average of 0.4-0.6%) and maximum percent in the standard, separately. 1 % Zr amount has been achieved via Zirmax (66.7 Mg-33.3 Zr) master alloy addition. The ultimate tensile strength of ZE41A with 1% Zr has been increased up to about 220-225 MPa in comparison to 200 MPa given in AMS 4439. The reason for the increase in strength with the addition of Zirmax is based on the decrease in grain size, which was measured about 30 µm. Optical microscope, scanning electron microscopy (SEM) and X-ray Diffraction (XRD) were used to detect the change in the microstructural futures via alloying. The zirconium rich coring at the center of the grains was observed in addition to the grain boundary intermetallic phases and bulk Mg-rich matrix. The solidification characteristics were also identified by using the cooling curve obtained from the sand casting mold during cooling of the alloys.

Keywords: aerospace, grain refinement, magnesium, sand casting, ZE41A

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Authors: Divya Singh, Avinash Parashar

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Due to superior mechanical, creep and nuclear cross section, zirconium and niobium (Zr-Nb) based alloys are commonly used as nuclear materials for the manufacturing of fuel cladding and pressure tubes in nuclear power plants. In this work, symmetrical tilt grain boundary (STGB) structures in α-Zr are studied for their structure and energies along two tilt axes- [0001] and [0-110] using MD based simulations. Tilt grain boundaries are obtained along [0001] tilt axis, and special twin structures are obtained along [0-110] tilt axis in α-Zr. For Nb, STGBs are constructed along [100] and [110] axis using atomistic simulations. The correlation between GB structures and their energies is subsequently examined. A close relationship is found to exist between individual GB structure and its energy in both α-Zr and Nb. It is also concluded that the energies of the more coherent twin grain boundaries are lower than the symmetrical tilt grain boundaries.

Keywords: grain boundaries, molecular dynamics, grain boundary energy, hcp crystal

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Authors: S. M. A. Al-Qawabah, A. I. O. Zaid

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Aluminum and its alloys are versatile materials which are widely used in industrial and engineering applications due to their good and useful properties e.g. high strength to weight ratio, high thermal and electrical conductivities and good resistance to corrosion. However, against these favorable properties they have the disadvantage they solidifying large grain columnar structure which negatively affects their mechanical properties and surface quality. Aluminum alloys are normally grain refined by some alloying elements, such as Ti, Ti-B or Zr. In this paper, the effect of zirconium addition to Al grain refined by Ti after extrusion on its wear resistance is investigated under different loads and sliding speeds namely at 5,10 and 20 N loads and sliding speeds ranging from m/min. and m/min. the results are presented in three-dimensional wear mode. To the best the authors' knowledge, the wear of aluminum in 3-dimensions has never been tackled before. In this work, the wear resistance of by presenting the results of wear are presented and discussed on the time, load and speed plots.

Keywords: aluminum grain refined, addition of titanium, wear resistance, titanium

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Authors: Ruqia Nazir, Robin Perutz

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Collision-induced dissociation (CID) can be used to study the intrinsic properties of ions in the gas phase.1 Decay pathways of transition metal difluoride complexes of titanium, zirconium, hafnium, and ruthenium were studied by CID in an ESI-Ion trap mass spectrometer. Furthermore, the decay pathways of multiply charged anions (MCAs) of titanium and zirconium were also studied. The CID results are illustrated by the behaviour of (Cp*)₂TiF₂, which initially forms the ions [M-F-]⁺, [M+Na]⁺, and [M+K]⁺. The [(Cp*₂)TiF⁺ ion decays on resonant excitation to lose HF forming [Cp*(C₅Me₄CH₂)Ti]⁺ (Figure). The other major ion, [(Cp*)₂TiF₂+Na]⁺, decays on resonant excitation with production of [(Cp*)₂TiF₂]⁺ and [C₅Me₄CH₂]⁺. We also report the behaviour of Cp₂MF₂ (M = Zr, Hf) and Ru(PMe₃)₄F₂. The decay pathway of the multiply charged anions (MCAs), notably TiF₆²⁻ and ZrF₆²⁻ was concluded to be ionic fragmentation with loss of F⁻ rather than electron detachment.

Keywords: collision induced dissociation, transition metal difluoride comolexes, multiply charged anions, mass spectrometry

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Authors: Erdinç Vural, Bülent Özdalyan, Serkan Özel

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The four-stroke single cylinder diesel engine has been used in this study, the pistons and valves of the engine have been stabilized, the aluminum oxide (Al₂O₃) in different ratios has been added in the power of zirconium (ZrO₂) magnesium oxide (MgO), and has been coated with the plasma spray method. The pistons and valves of the combustion chamber of the engine are coated with 5 different (ZrO₂ + MgO), (ZrO₂ + MgO + 25% Al₂O₃), (ZrO₂ + MgO + 50% Al₂O₃), (ZrO₂ + MgO + 75% Al₂O₃), (Al₂O₃) sample. The material tests have been made for each of the coated engine parts with the scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) using Cu Kα radiation surface analysis methods. The engine tests have been repeated for each sample in any electric dynamometer in full power 1600 rpm, 2000 rpm, 2400 rpm and 2800 rpm engine speeds. The material analysis and engine tests have shown that the best performance has been performed with (ZrO₂ + MgO + 50% Al₂O₃). Thus, there is no significant change in HC and Smoke emissions, but NOx emission is increased, as the engine improves power, torque, specific fuel consumption and CO emissions in the tests made with sample A3.

Keywords: ceramic coating, material characterization, engine performance, exhaust emissions

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Authors: Alexia Wu, Joel Ribis, Jean-Christophe Brachet, Emmanuel Clouet, Benoit Arnal, Elodie Rouesne, Stéphane Urvoy, Justine Roubaud, Yves Serruys, Frederic Lepretre

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To enhance the safety of Light Water Reactor, accident tolerant fuel (ATF) claddings materials are under development. In the framework of CEA-AREVA-EDF collaborative program on ATF cladding materials, CEA has engaged specific studies on chromium coated zirconium alloys. Especially for Loss-of-Coolant-Accident situations, chromium coated claddings have shown some additional 'coping' time before achieving full embrittlement of the oxidized cladding, when compared to uncoated references – both tested in steam environment up to 1300°C. Nevertheless, the behavior of chromium coatings and the stability of the Zr-Cr interface under neutron irradiation remain unknown. Two main points are addressed: 1. Bulk Cr behavior under irradiation: Due to its BCC crystallographic structure, Cr is prone to Ductile-to-Brittle-Transition at quite high temperature. Irradiation could be responsible for a significant additional DBTT shift towards higher temperatures. 2. Zircaloy/Cr interface behavior under irradiation: Preliminary TEM examinations of un-irradiated samples revealed a singular Zircaloy-4/Cr interface with nanometric intermetallic phase layers. Such particular interfaces highlight questions of how they would behave under irradiation - intermetallic zirconium phases are known to be more or less stable under irradiations. Another concern is a potential enhancement of chromium diffusion into the zirconium-alpha based substrate. The purpose of this study is then to determine the behavior of such coatings after ion irradiations, as a surrogate to neutron irradiation. Ion irradiations were performed at the Jannus-Saclay facility (France). 20 MeV Kr8+ ions at 400°C with a flux of 2.8x1011 ions.cm-2.s-1 were used to irradiate chromium coatings of 1-2 µm thick on Zircaloy-4 sheets substrate. At the interface, the calculated damage is close to 10 dpa (SRIM, Quick Calculation Damage mode). Thin foil samples were prepared with FIB for both as-received and irradiated coated samples. Transmission Electron Microscopy (TEM) and in-situ tensile tests in a Scanning Electron Microscope are being used to characterize the un-irradiated and irradiated materials. High Resolution TEM highlights a great complexity of the interface before irradiation since it is formed of an alternation of intermetallic phases – C14 and C15. The interfaces formed by these intermetallic phases with chromium and zirconium show semi-coherency. Chemical analysis performed before irradiation shows some iron enrichment at the interface. The chromium coating bulk microstructures and properties are also studied before and after irradiation. On-going in-situ tensile tests focus on the capacity of chromium coatings to sustain some plastic deformation when tested up to 350°C. The stability of the Cr/Zr interface is shown after ion irradiation up to 10 dpa. This observation constitutes the first result after irradiation on these new coated claddings materials.

Keywords: accident tolerant fuel, HRTEM, interface, ion-irradiation

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Authors: Bharat Kumar, Deepak Kumar, Vijay Chaudhry

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Zirconium alloys are widely used for the core components of a pressurized heavy water reactor (PHWR) or Canada deuterium (CANDU) reactor due to their low neutron absorption cross-section and excellent mechanical properties. The components made of Zirconium alloys are subjected to flow-induced vibrations, resulting in fretting wear at the interface of; pressure tubes and bearing pads, pressure tubes and calandria tubes, and calandria tubes and Liquid injection shutdown system (LISS) nozzles. There is a need to explore the tribological response under such conditions. Present work simulates the contact between calandria tube and LISS nozzle of PHWR/CANDU reactor as cylinder-on-cylinder contact configuration. Reciprocating tribo-tests were conducted on Zircaloy-4 (Zr-4) under the self-mated condition at varying amplitude, frequency, and sliding time. To understand the active wear mechanism, worn surfaces were analyzed using Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The change in amplitude severely affects the wear than other factors. The wear mechanism transits from adhesion to abrasion with increasing test amplitude. The dominant wear mechanisms are micro-cutting and micro-plowing followed by delamination in some areas. However, the coefficient of friction has indifferent behaviors.

Keywords: zircaloy-4, tribology, calandria tube, LISS nozzle, PHWR

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Authors: Jefri Draup, Antoine Ambard, Chi-Toan Nguyen

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Zirconium alloys exhibit solid-state phase transformations under thermal loading. These can lead to a significant evolution of the microstructure and associated mechanical properties of materials used in nuclear fuel cladding structures. Therefore, the ability to capture effects of phase transformation on the material constitutive behavior is of interest during conditions of severe transient thermal loading. Whilst typical Avrami, or Johnson-Mehl-Avrami-Kolmogorov (JMAK), type models for phase transformations have been shown to have a good correlation with the behavior of Zircaloy-4 under constant heating rates, the effects of variable and fast heating rates are not fully explored. The present study utilises the results of in-situ high energy synchrotron X-ray diffraction (SXRD) measurements in order to validate the phase transformation models for Zircaloy-4 under fast variable heating rates. These models are used to assess the performance of fuel cladding structures under loss of coolant accident (LOCA) scenarios. The results indicate that simple Avrami type models can provide a reasonable indication of the phase distribution in experimental test specimens under variable fast thermal loading. However, the accuracy of these models deteriorates under the faster heating regimes, i.e., 100Cs⁻¹. The studies highlight areas for improvement of simple Avrami type models, such as the inclusion of temperature rate dependence of the JMAK n-exponent.

Keywords: accident, fuel, modelling, zirconium

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Authors: Guanyu Jiang, Donghai Xu, Huanteng Liu

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After the Fukushima-Daiichi accident, the development of accident tolerant fuel cladding materials to improve reactor safety has become a hot topic in the field of nuclear industry. ZrO₂ has a satisfactory neutron economy and can guarantee the fission chain reaction process, which enables it to be a promising coating for zirconium alloy cladding. Maintaining a good corrosion resistance in primary coolant loop during normal operations of Pressurized Water Reactors is a prerequisite for ZrO₂ as a protective coating on zirconium alloy cladding. Research on the corrosion performance of ZrO₂ coating in nuclear water chemistry is relatively scarce, and existing reports failed to provide an in-depth explanation for the failure causes of ZrO₂ coating. Herein, a detailed corrosion process of ZrO₂ coating in lithiated water at 360 °C and 18.5 MPa was proposed based on experimental research and molecular dynamics simulation. Lithiated water with different LiOH solutions in the present work was deaerated and had a dissolved oxygen concentration of < 10 ppb. The concentration of Li (as LiOH) was determined to be 2.3 ppm, 70 ppm, and 500 ppm, respectively. Corrosion tests were conducted in a static autoclave. Modeling and corresponding calculations were operated on Materials Studio software. The calculation of adsorption energy and dynamics parameters were undertaken by the Energy task and Dynamics task of the Forcite module, respectively. The protective effect and failure mechanism of ZrO₂ coating on Zry-4 under varied LiOH concentrations was further revealed by comparison with the coating corrosion performance in pure water (namely 0 ppm Li). ZrO₂ coating provided a favorable corrosion protection with the occurrence of localized corrosion at low LiOH concentrations. Factors influencing corrosion resistance mainly include pitting corrosion extension, enhanced Li+ permeation, short-circuit diffusion of O²⁻ and ZrO₂ phase transformation. In highly-concentrated LiOH solutions, intergranular corrosion, internal oxidation, and perforation resulted in coating failure. Zr ions were released to coating surface to form flocculent ZrO₂ and ZrO₂ clusters due to the strong diffusion and dissolution tendency of α-Zr in the Zry-4 substrate. Considering that primary water of Pressurized Water Reactors usually includes 2.3 ppm Li, the stability of ZrO₂ make itself a candidate fuel cladding coating material. Under unfavorable conditions with high Li concentrations, more boric acid should be added to alleviate caustic corrosion of ZrO₂ coating once it is used. This work can provide some references to understand the service behavior of nuclear coatings under variable water chemistry conditions and promote the in-pile application of ZrO₂ coating.

Keywords: ZrO₂ coating, Zry-4, corrosion behavior, failure mechanism, LiOH concentration

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Authors: Sylwia Gieraltowska, Lukasz Wachnicki, Bartlomiej S. Witkowski, Marek Godlewski

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Oxide layers doped with rare-earth (RE) ions in optimized way can absorb short (ultraviolet light), which will be converted to visible light by so-called down-conversion. Down-conversion mechanisms are usually exploited to modify the incident solar spectrum. In down conversion, multiple low-energy photons are generated to exploit the energy of one incident high-energy photon. These RE-doped oxide materials have attracted a great deal of attention from researchers because of their potential for optical manipulation in optical devices (detectors, temperature sensors, and compact solid-state lasers, light-emitting diodes), bio-analysis, medical therapy, display technologies, and light harvesting (such as in photovoltaic cells). The zirconium dioxide (ZrO2) doped RE ions (Eu, Tb, Ce) multilayer structures were tested as active layers, which can convert short wave emission to light in the visible range (the down-conversion mechanism). For these applications original approach of deposition ZrO2 layers using the Atomic Layer Deposition (ALD) method and doping these layers with RE ions using the spin-coating technique was used. ALD films are deposited at relatively low temperature (well below 250°C). This can be an effective method to achieve the white-light emission and to improve on this way light conversion efficiency, by an extension of absorbed spectral range by a solar cell material. Photoluminescence (PL), X-ray diffraction (XRD), scanning electron microscope (SEM) and atomic force microscope (AFM) measurement are analyzed. The research was financially supported by the National Science Centre (decision No. DEC-2012/06/A/ST7/00398 and DEC- 2013/09/N/ST5/00901).

Keywords: ALD, oxide layers, photovoltaics, thin films

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Authors: Hossein Anaraki-Ardakani

Abstract:

A green and efficient one-pot synthesis of benzylamino coumarin derivatives by a three-component condensation of 4-hydroxycoumarin, cyclic secondary amine, and aromatic aldehyde in the presence of ZrO2 nanoparticles (NPs) as a heterogeneous catalyst in water at room temperature has been reported.

Keywords: 3-benzyl substituted coumarin derivative, ZrO2 nanoparticles (NPs), green synthesis, multicomponent reaction

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Authors: Raphaelle Guillou, Matthieu Le Saux, Jean-Christophe Brachet, Thomas Guilbert, Elodie Rouesne, Denis Menut, Caroline Toffolon-Masclet, Dominique Thiaudiere

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In some hypothetical accidental situations, such as during a Loss Of Coolant Accident (LOCA) in pressurized water reactors, fuel cladding tubes made of zirconium alloys can be exposed for a few minutes to steam at High Temperature (HT up to 1200°C) before being cooled and then quenched in water. Under LOCA-like conditions, the cladding undergoes a number of metallurgical changes (phase transformations, oxygen diffusion and growth of an oxide layer...) and is consequently submitted to internal stresses whose state evolves during the transient. These stresses can have an effect on the oxide structure and the oxidation kinetics of the material. They evolve during cooling, owing to differences between the thermal expansion coefficients of the various phases and phase transformations of the metal and the oxide. These stresses may result in the failure of the cladding during quenching, once the material is embrittled by oxidation. In order to progress in the evaluation of these internal stresses, X-ray diffraction experiments were performed in-situ under synchrotron radiation during HT oxidation and subsequent cooling on Zircaloy-4 sheet samples. First, structural evolutions, such as phase transformations, have been studied as a function of temperature for both the oxide layer and the metallic substrate. Then, internal stresses generated within the material oxidized at temperatures between 700 and 900°C have been evaluated thanks to the 2θ diffraction peak position shift measured during the in-situ experiments. Electron backscatter diffraction (EBSD) analysis was performed on the samples after cooling in order to characterize their crystallographic texture. Furthermore, macroscopic strains induced by oxidation in the conditions investigated during the in-situ X-ray diffraction experiments were measured in-situ in a dilatometer.

Keywords: APRP, stains measurements, synchrotron diffraction, zirconium allows

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Authors: Kenichi Hirota, Jifeng Wang, Sadao Araki, Koji Endo, Hideki Yamamoto

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Zirconium (Zr) has been used as a fuel cladding tube for nuclear reactors, because of the excellent corrosion resistance and the low adsorptive material for neutron. Generally speaking, the natural resource of Zr is often containing Hf that has similar properties. The content of Hf in the Zr resources is about 2~4 wt%. In the industrial use, the content of Hf in Zr resources should be lower than the 100 ppm. However, the separation of Zr and Hf is not so easy, because of similar chemical and physical properties such as melting point, boiling point and things. Solvent extraction method has been applied for the separation of Zr and Hf from Zr natural resources. This method can separate Hf with high efficiency (Hf < 100ppm), however, it needs much amount of organic solvents for solvent extraction and the cost of its disposal treatment is high. Therefore, we attached attention for the fractional crystallization. This separation method depends on the solubility difference of Zr and Hf in the solvent. In this work, hexafluorozirconate (hafnate) (K2Zr(Hf)F6) was used as model compound. Solubility of K2ZrF6 in water showed lower than that of K2HfF6. By repeating of this treatment, it is possible to purify Zr, practically. In this case, 16-18 times of recrystallization stages were needed for its high purification. The improvement of the crystallization process was carried out in this work. Water, hydrofluoric acid (HF) and hydrofluoric acid (HF) +hydrochloric acid (HCl) mixture were chosen as solvent for dissolution of Zr and Hf. In the experiment, 10g of K2ZrF6 was added to each solvent of 100mL. Each solution was heated for 1 hour at 353K. After 1h of this operation, they were cooled down till 293K, and were held for 5 hours at 273K. Concentration of Zr or Hf was measured using ICP analysis. It was found that Hf was separated from Zr-Hf mixed compound with high efficiency, when HF-HCl solution was used for solvent of crystallization. From the comparison of the particle size of each crystal by SEM, it was confirmed that the particle diameter of the crystal showed smaller size with decreasing of Hf content. This paper concerned with purification of Zr from Zr-Hf mixture using crystallization method.

Keywords: crystallization, zirconium, hafnium, separation

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Authors: Jung-Ho Moon, Tae Kwon Ha

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In the present study, the effect of Si, Al, Ti, Zr, and Nb addition on the microstructure and hot workability of cast M42 tool steels, basically consisting of 1.0C, 0.2Mn, 3.8Cr, 1.5W, 8.5Co, 9.2Mo, and 1.0V in weight percent has been investigated. Tool steels containing Si of 0.25 and 0.5 wt.%, Al of 0.06 and 0.12 wt.%, Ti of 0.3 wt.%, Zr of 0.3 wt.%, and Nb of 0.3 wt.% were cast into ingots of 140 mm´ 140 mm´ 330 mm by vacuum induction melting. After solution treatment at 1150°C for 1.5 hrs. followed by furnace cooling, hot rolling at 1180 °C was conducted on the ingots. Addition of titanium, zirconium and niobium was found to retard the decomposition of the eutectic carbides and result in the deterioration of hot workability of the tool steels, while addition of aluminium and silicon showed relatively well decomposed carbide structure and resulted in sound hot rolled plates.

Keywords: high speed steels, alloying elements, eutectic carbides, microstructure, hot workability

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Authors: Jeonho Moon, Tae Kwon Ha

Abstract:

In the present study, the effect of Si, Al, Ti, Zr, and Nb addition on the microstructure and hot workability of cast M42 tool steels, basically consisting of 1.0 C, 0.2 Mn, 3.8 Cr, 1.5 W, 8.5 Co, 9.2 Mo, and 1.0 V in weight percent has been investigated. Tool steels containing Si of 0.25 and 0.5 wt.%, Al of 0.06 and 0.12 wt.%, Ti of 0.3 wt.%, Zr of 0.3 wt.%, and Nb of 0.3wt.% were cast into ingots of 140 mm x 140 mm x 330 mm by vacuum induction melting. After solution treatment at 1150 °C for 1.5 hr followed by furnace cooling, hot rolling at 1180 °C was conducted on the ingots. Addition of titanium, zirconium and niobium was found to retard the decomposition of the eutectic carbides and result in the deterioration of hot workability of the tool steels, while addition of aluminum and silicon showed relatively well decomposed carbide structure and resulted in sound hot rolled plates.

Keywords: duplex stainless steel, alloying elements, eutectic carbides, microstructure, hot workability

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Authors: B. M. Patil

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Calcium Zirconate (CaZrO3) has high protonic conductivities at elevated temperature in water or hydrogen atmosphere. Undoped calcium zirconate acts as a p-type semiconductor in air. In this paper, we reported synthesis of CaZrO3 nanoparticles via modified molecular precursor method. The precursor calcium zirconium oxalate (CZO) was synthesized by exchange reaction between freshly generated aqueous solution of sodium zirconyl oxalate and calcium acetate at room temperature. The controlled pyrolysis of CZO in air at 700°C for one hour resulted in the formation nanocrystalline CaZrO3 powder. CaZrO3 obtained by the present method was characterized by Simultaneous thermogravimetry and differential thermogravimetry (TG-DTA), X-ray diffraction (XRD), infra-red spectroscopy and transmission electron microscopy (TEM). The pellets of synthesized CaZrO3 fabricated, sintered at 1000°C for 5 hr and tested as sensors for NO2 and NH3 gases.

Keywords: CaZrO3, CZO, NO2, NH3

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Authors: A. Boveiri Monji, H. Yousefnia, M. Haji Hosseini, S. Zolghadri

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A clean spectrophotometric method for the determination of hafnium by using a green reagent, acidic extract of Ficus carica tree leaves is developed. In 6-M hydrochloric acid, hafnium reacts with this reagent to form a yellow product. The formed product shows maximum absorbance at 421 nm with a molar absorptivity value of 0.28 × 104 l mol⁻¹ cm⁻¹, and the method was linear in the 2-11 µg ml⁻¹ concentration range. The detection limit value was found to be 0.312 µg ml⁻¹. Except zirconium and iron, the selectivity was good, and most of the ions did not show any significant spectral interference at concentrations up to several hundred times. The proposed method was green, simple, low cost, and selective.

Keywords: spectrophotometric determination, Ficus caricatree leaves, synthetic reagents, hafnium

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Authors: Damien Rinsant, Eugen Andreiadis, Michael Carboni, Daniel Meyer

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Different types of materials have been developed for the solid/liquid uranium extraction processes, such as functionalized organic polymers, hybrid silica or inorganic adsorbents. In general, these materials exhibit a moderate affinity for uranyl ions and poor selectivity against impurities like iron, vanadium or molybdenum. Moreover, the structural organization deficiency of these materials generates ion diffusion issues inside the material. Therefore, the aim of our study is to developed efficient and organized materials, stable in the acid media encountered in uranium extraction processes. Metal organic frameworks (MOFs) are hybrid crystalline materials consisting of an inorganic part (cluster or metal ions) and tailored organic linkers connected via coordination bonds. These hierarchical materials have exceptional surface area, thermal stability and a large variety of tunable structures. However, due to the reversibility of constitutive coordination bonds, MOFs have moderate stability in strongly complexing or acidic media. Only few of them are known to be stable in aqueous media and only one example is described in strong acidic media. However, these conditions are very often encountered in the environmental pollution remediation of mine wastewaters. To tackle the challenge of developing MOFs adapted for uranium extraction from acid mine waters, we have investigated the stability of several materials. To ensure a good stability we have synthetized and characterized different materials based on highly coordinated metal clusters, such as LnOFs and Zirconium based materials. Among the latter, the UiO family shows a great stability in sulfuric acid media even in the presence of 1.4 M sodium sulfate at pH 2. However, the stability in phosphoric media is reduced due to the high affinity between zirconium and phosphate ligand. Based on these results, we have developed a tertiary amine functionalized MOF denoted UiO-68-NMe2 particularly adapted for the extraction of anionic uranyl (VI) sulfate complexes mainly present in the acid mine solutions. The adsorption capacity of the material has been determined upon varying total sulfate concentration, contact time and uranium concentration. The extraction tests put in evidence different phenomena due to the complexity of the extraction media and the interaction between the MOF and sulfate anion. Finally, the extraction mechanisms and the interaction between uranyl and the MOF structure have been investigated. The functionalized material UiO-68-NMe2 has been characterized in the presence and absence of uranium by FT-IR, UV and Raman techniques. Moreover, the stability of the protonated amino functionalized MOF has been evaluated. The synthesis, characterization and evaluation of this type of hybrid material, particularly adapted for uranium extraction in sulfuric acid media by an anionic exchange mechanism, paved the way for the development of metal organic frameworks functionalized by different other chelating motifs, such as bifunctional ligands showing an enhanced affinity and selectivity for uranium in acid and complexing media. Work in this direction is currently in progress.

Keywords: extraction, MOF, ligand, uranium

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