Email this article 
E-beam sintering of neodymium tungstate and its composite with nickel (II) and copper (II) oxides
Abstract
Neodymium tungstates and their composites with metal alloys, such as NiCu, have emerged as promising materials for hydrogen separation membranes due to their high proton conductivity and stability in CO2-containing atmospheres. The fabrication of gas-tight ceramics based on these materials constitutes a distinct challenge. A promising approach to address this issue is the utilization of advanced sintering techniques, such as radiation-thermal sintering using an electron beam. The present study investigates the impact of radiation-thermal sintering temperature on the structural, textural properties, hydration ability, and oxygen mobility of Nd5.5WO11.25−δ oxides and NiO–CuO–Nd5.5WO11.25−δ composites, the precursors of NiCu alloy – Nd5.5WO11.25−δ materials for hydrogen separation membranes. The main phase of the Nd5.5WO11.25−δ samples is defective double fluorite, while their composites contain various nickel and copper oxides along with the neodymium tungstate phase. The attainment of gas-tightness in Nd5.5WO11.25−δ samples is achieved even at relatively low sintering temperatures (1200–1300 °C), which is unattainable through sintering in a furnace. Conversely, the composite samples exhibit high porosity. Hence, the procedure of preparing the NiO–CuO–Nd5.5WO11.25−δ composites required further optimization. Nd5.5WO11.25−δ sintered by e-beam at 1100–1300 °C exhibit optimal hydration properties. The highest oxygen mobility is demonstrated for the samples sintered at 1100 and 1200 °C (D* up to ~ 10−8 cm2/s), which is promising in the context of the incorporation and transport of protons in hydrogen separation membranes. Consequently, e-beam sintering emerges as a promising method for producing proton conductive ceramics based on Nd tungstate.
Keywords
Full Text:
PDFReferences
Amin Md, Butt AS, Ahmad J, Lee C, et al., Issues and challenges in hydrogen separation technologies, Energy Rep., 9 (2023) 894–911. https://doi.org/10.1016/j.egyr.2022.12.014
Singla S, Shetti NP, Basu S, Mondal K, et al., Hydrogen production technologies-Membrane based separation, storage and challenges, J. Environ. Manage., 302A (2022) 113963. https://doi.org/10.1016/j.jenvman.2021.113963
Mukhina E, Gonde A, Mukhametdinova A, Askarova A, et al., An overview of H2 separation membranes for harsh conditions with a downhole design for in-situ generation, Int. J. Hydrogen Energy, 205 (2026) 153335. https://doi.org/10.1016/j.ijhydene.2025.153335
Cheng H, Dual-phase mixed protonic-electronic conducting hydrogen separation membranes: A review, Membranes, 12(7) (2022) 647. https://doi.org/10.3390/membranes12070647
Matkin D, Medvedev D, Yang G, Formation of protonic defects in complex oxides: Fundamentals and methodological considerations of hydration, Energy Rev., 5(1) (2026) 100179. https://doi.org/10.1016/j.enrev.2026.100179
Pikalova EYu, Progress in infiltration technology applied to air electrodes with proton-conducting electrolyte backbones, Electrochem. Mater. Technol., 4(2) (2025) 20254054. https://doi.org/10.15826/elmattech.2025.4.054
Lu Q, Zhang Y, Zhao H, Lee PS, et al., Emerging materials and future strategies for solid oxide electrochemical cells, Adv. Energy Mater., (2026) e06791. https://doi.org/10.1002/aenm.202506791
Akopian M, Medvedev D, Heavily doped proton-conducting perovskites: Relationships between defect structure and functional properties, Chim. Tech. Acta, 13(3) (2026) 9769. https://doi.org/10.15826/chimtech.9769
de Souza ECC, Muccillo R, Properties and applications of perovskite proton conductors, Mat. Res., 13(3) (2010) 385–394. https://doi.org/10.1590/S1516-14392010000300018
Kreuer KD, Adams St, Münch W, Fuchs A, et al., Proton conducting alkaline earth zirconates and titanates for high drain electrochemical applications, Solid State Ionics, 145(1–4) (2001) 295–306. https://doi.org/10.1016/S0167-2738(01)00953-5
Ryu KH, Haile SM, Chemical stability and proton conductivity of doped BaCeO3–BaZrO3 solid solutions, Solid State Ionics, 125(1–4) (1999) 355–367. https://doi.org/10.1016/S0167-2738(99)00196-4
Bhide SV, Virkar AV, Stability of BaCeO3‐based proton conductors in water‐containing atmospheres, J. Electrochem. Soc., 146(6) (1999) 2038–2044. https://doi.org/10.1149/1.1391888
Kannan R, Singh K, Gill S, Fürstenhaup T, Chemically stable proton conducting doped BaCeO3 – No more fear to SOFC wastes, Sci. Rep., 3 (2013) 2138. https://doi.org/10.1038/srep02138
Alami AH, Alashkar A, Abdelkareem MA, Rezk H, et al., Perovskite membranes: Advancements and challenges in gas separation, production, and capture, Membranes, 13(7) (2023) 661. https://doi.org/10.3390/membranes13070661
Rashid NLRM, Samat AA, Jais AA, Somalu MR, et al., Review on zirconate-cerate-based electrolytes for proton-conducting solid oxide fuel cell, Ceram. Int., 45(6) (2019) 6605–6615. https://doi.org/10.1016/j.ceramint.2019.01.045
Cheng H, Rare earth tungstate: One competitive proton conducting material used for hydrogen separation: A review, Separations, 10(5) (2023) 317. https://doi.org/10.3390/separations10050317
Shlyakhtina AV, Shcherbakova LG, Savvin SN, Núñez P, et al., Electrical conductivity of Ln6–xZrxMoO12+δ (Ln = La, Nd, Sm; x = 0.2, 0.6) ceramics during thermal cycling, Inorg. Mater., 52(10) (2016) 1055–1062. https://doi.org/10.1134/S0020168516100149
Shlyakhtina AV, Savvin SN, Lyskov NV, Kolbanev IV, et al., Polymorphism in the family of Ln6−xMoO12−δ (Ln = La, Gd–Lu; x = 0, 0.5) oxygen ion- and proton-conducting materials, J. Mater. Chem. A, 5(16) (2017) 7618–7630. https://doi.org/10.1039/C6TA09963G
Escolástico S, Balaguer M, Solís C, Toldrá-Reig F, et al., Promotion of mixed protonic–electronic transport in La5.4WO11.1−δ membranes under H2S atmospheres, J. Mater. Chem. A, 11(32) (2023) 17246–17256. https://doi.org/10.1039/D3TA01827J
Escolástico S, Serra JM, Nd5.5W1−xUxO11.25−δ system: Electrochemical characterization and hydrogen permeation study, J. Membr. Sci., 489 (2015) 112–118. https://doi.org/10.1016/j.memsci.2015.04.017
Escolástico S, Solís C, Haugsrud R, Magrasó A, et al., On the ionic character of H2 separation through mixed conducting Nd5.5W0.5Mo0.5O11.25−δ membrane, Int. J. Hydrogen Energy, 42(16) (2017) 11392–11399. https://doi.org/10.1016/j.ijhydene.2017.02.087
Magrasó A, Haugsrud R, Effects of the La/W ratio and doping on the structure, defect structure, stability and functional properties of proton-conducting lanthanum tungstate La28−xW4+xO54+δ. A review, J. Mater. Chem. A, 2(32) (2014) 12630–12641. https://doi.org/10.1039/c4ta00546e
Jayalekshmy NL, John A, Thomas JK, Solomon S, Structural, optical and electrical characterizations of Ln6WO12 (Ln = La, Nd, Sm, Gd) nanoceramics, Appl. Phys. A, 125(2) (2019) 143. https://doi.org/10.1007/s00339-019-2441-z
Shlyakhtina AV, Avdeev M, Abrantes JCC, Gomes E, et al., Structure and conductivity of Nd6MoO12-based potential electron–proton conductors under dry and wet redox conditions, Inorg. Chem. Front., 6(2) (2019) 566–575. https://doi.org/10.1039/c8qi01142g
Haugsrud R, Kjølseth C, Effects of protons and acceptor substitution on the electrical conductivity of La6WO12, J. Phys. Chem. Solids, 69(7) (2008) 1758–1765. https://doi.org/10.1016/j.jpcs.2008.01.002
Sánchez-Caballero A, Porras-Vázquez JM, dos Santos-Gómez L, Zamudio-García J, et al., Structure and mixed proton–electronic conductivity in Pr and Nb-substituted La5.4MoO12−δ ceramics, Materials, 18(3) (2025) 529. https://doi.org/10.3390/ma18030529
Bespalko Yu, Eremeev N, Skryabin P, Krieger T, et al., Structural and transport properties of neodymium tungstates prepared via mechanochemical activation, Ceram. Int., 45(7B) (2019) 9529–9536. https://doi.org/10.1016/j.ceramint.2018.09.277
Bespalko Yu, Sadykov V, Eremeev N, Skryabin P, et al., Synthesis of tungstates/Ni0.5Cu0.5O nanocomposite materials for hydrogen separation cermet membranes, Compos. Struct., 202 (2018) 1263–1274. https://doi.org/10.1016/j.compstruct.2018.06.004
Eremeev NF, Bespalko YuN, Sadovskaya EM, Skriabin PI, et al., Structural and transport properties of Nd tungstates and their composites with Ni0.5Cu0.5O obtained by mechanical activation, Dalton Trans., 51(19) (2022) 7705–7714. https://doi.org/10.1039/d2dt00498d
Eremeev N, Krasnov A, Bespalko Yu, Bobrova L, et al., An experimental performance study of a catalytic membrane reactor for ethanol steam reforming over a metal honeycomb catalyst, Membranes, 11(10) (2021) 790. https://doi.org/10.3390/membranes11100790
Völkl J, Alefeld G. Diffusion of hydrogen in metals. In: Hydrogen in Metals I. Springer: Berlin, Heidelberg; 2005. pp. 321–348. https://doi.org/10.1007/3540087052_51
Turnbull A, Ballinger RG, Hwang IS, Morra MM, et al., Hydrogen transport in nickel-base alloys, Metall. Trans. A, 23(1S) (1992) 3231–3244. https://doi.org/10.1007/BF02663432
Lu X, Díaz A, Ma J, Wang D, et al., The effect of plastic deformation on hydrogen diffusion in nickel Alloy 625, Scripta Mater., 223 (2023) 115210. https://doi.org/10.1016/j.scriptamat.2022.115210
Eremeev N, Altynbekova D, Valeev K, Krieger T, et al., Hydrogen production by dry reforming of methane in a catalytic reactor with La niobate-based hydrogen separation membrane, Chim. Tech. Acta, 12(3) (2025) 12311. https://doi.org/10.15826/chimtech.2025.12.3.11
Dubois C, Monty C, Philibert J, Oxygen self-diffusion in NiO single crystals, Philos. Mag. A, 46(3) (1982) 419–433. https://doi.org/10.1080/01418618208239569
Doornkamp C, Clement M, Ponec V, The isotopic exchange reaction of oxygen on metal oxides, J. Catal., 182(2) (1999) 390–399. https://doi.org/10.1006/jcat.1998.2377
Escolástico S, Stournari V, Malzbender J, Haas-Santo K, et al., Chemical stability in H2S and creep characterization of the mixed protonic conductor Nd5.5WO11.25−δ, Int. J. Hydrogen Energy, 43(17) (2018) 8342–8354. https://doi.org/10.1016/j.ijhydene.2018.03.060
Lyakhov NZ, Boldyrev VV, Voronin AP, Gribkov OS, et al., Electron beam stimulated chemical reaction in solids, J. Therm. Anal., 43(1) (1995) 21–31. https://doi.org/10.1007/BF02635965
Boldyrev VV, Voronin AP, Gribkov OS, Tkachenko EV, et al., Radiation-thermal synthesis. Current achievement and outlook, Solid State Ionics, 36(1–2) (1989) 1–6. https://doi.org/10.1016/0167-2738(89)90051-9
Annenkov YuM, Physical foundations for high-temperature electron-beam modification of ceramics, Russ. Phys. J., 39(11) (1996) 1146–1159. https://doi.org/10.1007/BF02436157
Eremeev N, Bespalko Yu, Mikhailenko M, Korobeynikov M, et al., Radiation-thermal sintering of oxide and composite materials for hydrogen energy by electron beam: A review, Electrochem. Mater. Technol., 4(4) (2025) 20254062. https://doi.org/10.15826/elmattech.2025.4.062
Sadykov V, Usoltsev V, Fedorova Yu, Mezentseva N, et al. Advanced sintering techniques in design of planar IT SOFC and supported oxygen separation membranes. In: Sintering of ceramics – New emerging techniques. Vienna: InTech; 2012. pp. 121–140. https://doi.org/10.5772/34958
Surzhikov AP, Frangulyan TA, Ghyngazov SA, Vasil’ev IP, et al., Sintering of zirconia ceramics by intense high-energy electron beam, Ceram. Int., 42(12) (2016) 13888–13892. https://doi.org/10.1016/j.ceramint.2016.05.198
Neronov VA, Voronin AP, Tatarintseva MI, Melekhova TE, et al., Sintering under a high-power electron beam, J. Less-Common Met., 117(1–2) (1986) 391–394. https://doi.org/10.1016/0022-5088(86)90065-2
Gonzalez-Martinez IG, Bachmatiuk A, Bezugly V, Kunstmann J, et al., Electron-beam induced synthesis of nanostructures: A review, Nanoscale, 8(22) (2016) 11340–11362. https://doi.org/10.1039/c6nr01941b
Auslender VL, Bochkarev IG, Boldyrev VV, Lyakhov NZ, et al., Electron beam induced diffusion controlled reaction in solids, Solid State Ionics, 101–103(1) (1997) 489–493. https://doi.org/10.1016/S0167-2738(97)84073-8
Zhang Y, Weber WJ, Ion irradiation and modification: The role of coupled electronic and nuclear energy dissipation and subsequent nonequilibrium processes in materials, Appl. Phys. Rev., 7(4) (2020) 041307. https://doi.org/10.1063/5.0027462
Pavlov YuS, Petrenko VV, Alekseev PA, Bystrov PA, et al., Trends and opportunities for the development of electron-beam energy-intensive technologies, Radiat. Phys. Chem., 198 (2022) 110199. https://doi.org/10.1016/j.radphyschem.2022.110199
Pikaev AK. Sovremennaya radiatsionnaya khimiya, Tom 1, Osnovnyye polozheniya, experimental’naya tekhnika i metody [Modern radiation chemistry, Volume 1, Basics, experimental techniques and methods]. Nauka: Moscow; 1985. 376 p. Russian.
Stepanov VA, Radiation-stimulated diffusion in solids, Tech. Phys., 43(8) (1998) 938–942. https://doi.org/10.1134/1.1259104
Ryazanov VV, Investigation of radiation-enhanced diffusion using first-passage time, Radiat. Phys. Chem., 203A (2023) 110608. https://doi.org/10.1016/j.radphyschem.2022.110608
Dienes GJ, Damask AC, Radiation enhanced diffusion in solids, J Appl Phys., 29(12) (1958) 1713–1721. https://doi.org/10.1063/1.1723032
Bourgoin JC, Corbett JW, Enhanced diffusion mechanisms, Radiat Effects, 36(3–4) (1978) 157–188. https://doi.org/10.1080/00337577808240846
Han X. A Systematic Study of Radiation Enhanced Diffusion; Theoretical Improvement and Application [dissertation]. Urbana (USA): University of Illinois Urbana-Champaign; 2014. 195 p.
Atas MS, The relationship between reinforcement ratio and e-beam irradiation in Y2O3 reinforced Al6061 alloys: A crystallographic assessment, Nucl. Instrum. Methods Phys. Res. B: Beam Interact. Mater. At., 548 (2024) 165252. https://doi.org/10.1016/j.nimb.2024.165252
Hobbs LW, Clinard Jr FW, Zinkle SJ, Ewing RC, Radiation effects in ceramics, J. Nucl. Mater., 216 (1994) 291–321. https://doi.org/10.1016/0022-3115(94)90017-5
Jiang N, Electron irradiation effects in transmission electron microscopy: Random displacements and collective migrations, Micron, 171 (2023) 103482. https://doi.org/10.1016/j.micron.2023.103482
Pikaev AK. Sovremennaya radiatsionnaya khimiya, Tom 3, Tvyordoye telo i polimery. Prikladnyye aspekty [Modern radiation chemistry, Volume 3, Solid state and polymers. Applied Aspects]. Nauka: Moscow; 1987. 448 p. Russian.
Gus’kov SYu, Kuchugov PA, Vergunova GA, Extreme matter compression caused by radiation cooling effect in gigabar shock wave driven by laser-accelerated fast electrons, Matter. Radiat. Extremes, 6(2) (2021) 020301. https://doi.org/10.1063/5.0026002
Dale Compton W, Arnold GW, Lattice displacements by fast electrons, J. Appl. Phys., 31(4) (1960) 621–625. https://doi.org/10.1063/1.1735653
Ohring M, Kasprzak L. Electronic charge-induced damage. In: Reliability and failure of electronic materials and devices. Academic Press, Elsevier: Amsterdam, Boston, Heidelberg, London, New York, Oxford, Paris, San Diego, San Francisco, Singapore, Sydney, Tokyo; 2015. pp. 327–385. https://doi.org/10.1016/B978-0-12-088574-9.00006-9
Eremeev N, Bespalko Yu, Sadovskaya E, Krieger T, et al., Structural and transport properties of La tungstate and its composite with nickel (II) – copper (II) oxide, Chim. Tech. Acta, 12(2) (2025) 12205. https://doi.org/10.15826/chimtech.2025.12.2.05
Ancharova UV, Mikhailenko MA, Tolochko BP, Lyakhov NZ, et al., Crystal phase structure investigation in the process of radiation-thermal transformations in systems SrO-Fe2O3, SrCO3-Fe2O3 (perovskite) and garnet Y2O3-Fe2O3, IOP Conf. Ser.: Mater. Sci. Eng., 11(1) (2016) 012110. https://doi.org/10.1088/1757-899X/110/1/012110
Klimov AS, Bakeev IYu, Oks EM, Tran VT, et al., Electron beam sintering of gradient Al2O3-ZrO2 ceramics with the forevacuum plasma electron source, J. Phys.: Conf. Ser., 1488(1) (2020) 012010. https://doi.org/10.1088/1742-6596/1488/1/012010
Sochugov NS, Soloviev AA, Shipilova AV, Rabotkin SV, et al., The effect of pulsed electron beam pretreatment of magnetron sputtered ZrO2:Y2O3 films on the performance of IT-SOFC, Solid State Ionics, 231 (2013) 11–17. https://doi.org/10.1016/j.ssi.2012.11.001
Mian MJ, Razmi J, Ladani L, Grain scale investigation of the mechanical anisotropic behavior of electron beam powder bed additively manufactured Ti6Al4V parts, Metals, 12(1) (2022) 163. https://doi.org/10.3390/met12010163
Sadykov V, Bespalko Yu, Sadovskaya E, Krieger T, et al., Structural and transport properties of e-beam sintered lanthanide tungstates and tungstates-molybdates, Nanomaterials, 12(19) (2022) 3282. https://doi.org/10.3390/nano12193282
Sadykov V, Pikalova E, Sadovskaya E, Shlyakhtina A, et al., Design of mixed ionic-electronic materials for permselective membranes and solid oxide fuel cells based on their oxygen and hydrogen mobility, Membranes, 13(8) (2023) 698. https://doi.org/10.3390/membranes13080698
Hegde RM, Kurkuri MD, Kigga M. Current scenario of nanocomposite materials for fuel cell applications. In: Sustainable Polymer Composites and Nanocomposites. Springer International Publishing: Cham, Switzerland; 2019. pp. 557–592. https://doi.org/10.1007/978-3-030-05399-4_20
Animitsa I, Neiman A, Sharafutdinov A, Nochrin S, Strontium tantalates with perovskite-related structure, Solid State Ionics, 136–137 (2000) 265–271. https://doi.org/10.1016/S0167-2738(00)00320-9
Xiang P, Ismail SA, Guo S, Jiang L, et al., Fluorite-based proton conducting oxides: Structures, materials and applications, Mater. Adv., 5(1) (2024) 12–29. https://doi.org/10.1039/d3ma00367a
Ryu JH, Yoon JW, Lim CS, Oh WC, et al., Microwave-assisted synthesis of nanocrystalline MWO4 (M: Ca, Ni) via water-based citrate complex precursor, Ceram. Int., 31(6) (2005) 883–888. https://doi.org/10.1016/j.ceramint.2004.09.015
Ancharova U, Mikhailenko M, Tolochko B, Lyakhov N, et al., Synthesis and staging of the phase formation for strontium ferrites in thermal and radiation-thermal reactions, IOP Conf. Ser.: Mater. Sci. Eng., 81(1) (2015) 012122. https://doi.org/10.1088/1757-899X/81/1/012122
HighScore Plus | XRD Analysis Software | Malvern Panalytical. Available from: https://www.malvernpanalytical.com/en/products/category/software/x-ray-diffraction-software/highscore-with-plus-option, Accessed on 6 August 2026
Biesinger MC, Accessing the robustness of adventitious carbon for charge referencing (correction) purposes in XPS analysis: Insights from a multi-user facility data review, Appl. Surf. Sci., 597 (2022) 153681. https://doi.org/10.1016/j.apsusc.2022.153681
Sadykov VA, Sadovskaya EM, Uvarov NF, Methods of isotopic relaxations for estimation of oxygen diffusion coefficients in solid electrolytes and materials with mixed ionic-electronic conductivity, Russ. J. Electrochem., 51(5) (2015) 458–467. https://doi.org/10.1134/S1023193515050109
Sadykov V, Sadovskaya E, Bobin A, Kharlamova T, et al., Temperature-programmed C18O2 SSITKA for powders of fast oxide-ion conductors: Estimation of oxygen self-diffusion coefficients, Solid State Ionics, 271 (2015) 69–72. https://doi.org/10.1016/j.ssi.2014.11.004
Sadykov V, Sadovskaya E, Eremeev N, Kolchugin A, et al., Novel materials based on Ruddlesden–Popper phases for solid oxide fuel cells and oxygen separation membranes: Fundamentals of oxygen transport, Chim. Tech. Acta, 12(3) (2025) 12304 https://doi.org/10.15826/chimtech.2025.12.3.04
Scherb T, Fantin A, Checchia S, Stephan-Scherb C, et al., Unravelling the crystal structure of Nd5.8WO12−δ and Nd5.7W0.75Mo0.25O12−δ mixed ionic electronic conductors, J. Appl. Cryst., 53(6) (2020) 1471–1483. https://doi.org/10.1107/S1600576720012698
Sadykov VA, Eremeev NF, Fedorova YuE, Krasnov AV, et al., Design and performance of asymmetric supported membranes for oxygen and hydrogen separation, Int. J. Hydrogen Energy, 46(38) (2021) 20222–20239. https://doi.org/10.1016/j.ijhydene.2020.01.106
Jiang N, Electron beam damage in oxides: A review, Rep. Prog. Phys., 79(1) (2016) 016501. https://doi.org/10.1088/0034-4885/79/1/016501
Stoneham AM, Radiation effects in insulators, Nucl. Instrum. Methods Phys. Res. B: Beam Interact. Mater. At., 91(1–4) (1994) 1–11. https://doi.org/10.1016/0168-583X(94)96184-0
Zhao P, Li L, Chen G, Guan X, et al., Structural evolution of low-dimensional metal oxide semiconductors under external stress, J. Semicond., 43(4) (2022) 041105. https://doi.org/10.1088/1674-4926/43/4/041105
Zhao L, Li L, Sheng H, Zheng H, et al., Atomistic insight into ordered defect superstructures at novel grain boundaries in CuO nanosheets: From structures to electronic properties, Nano Res., 12(5) (2019) 1099–1104. https://doi.org/10.1007/s12274-019-2354-3
Knotek ML, Feibelman PJ, Ion desorption by core-hole Auger decay, Phys. Rev. Lett., 40(14) (1978) 964–967. https://doi.org/10.1103/PhysRevLett.40.964
Niehus H, Losch W, ESD on metal oxides and oxygen adsorption layers: Evidence for different mechanisms in electron stimulated desorption, Surf. Sci., 111(2) (1981) 344–350. https://doi.org/10.1016/0039-6028(80)90713-X
Petford-Long AK, Long NJ, Safe limits for electron beam analysis of copper oxides, Ultramicroscopy, 34(1–2) (1990) 27–32. https://doi.org/10.1016/0304-3991(90)90053-O
Trunov VK, Tyushevskaya GI, Afonskii NS, Investigation of the double oxides formed in the reaction of Nd2O3, Sm2O3, and Er2O3 with tungsten (VI) oxide, Russ. J. Inorg. Chem., 13(4) (1968) 491–493.
Vijaya Kumar B, Velchuri R, Prasad G, Sreedhar B, et al., Preparation, characterization, photoactivity and XPS studies of Ln2ZrTiO7 (Ln = Sm and Nd), Ceram. Int., 36(4) (2010) 1347–1355. https://doi.org/10.1016/j.ceramint.2010.01.019
Quiñonero J, Pastor FJ, Orts JM, Gómez R, Photoelectrochemical behavior and computational insights for pristine and doped NdFeO3 thin-film photocathodes, ACS Appl. Mater. Interfaces, 13(12) (2021) 14150–14159. https://doi.org/10.1021/acsami.0c21792
Fiedor JN, Proctor A, Houalla M, Hercules DM, Study of the reduction behavior of W/TiO2 catalysts by XPS using curve fitting, deconvolution and factor analysis, Surf. Interface Anal., 23(4) (1995) 204–212. https://doi.org/10.1002/sia.740230403
Feng Z, McBriarty ME, Mane AU, Lu J, et al., Redox-driven atomic-scale changes in mixed catalysts: VOx/WOx/α-TiO2 (110), RSC Adv., 4(110) (2014) 64608–64616. https://doi.org/10.1039/c4ra14140g
Zeng X, Wang Z, Wang G, Gengenbach TR, et al., Highly dispersed TiO2 nanocrystals and WO3 nanorods on reduced graphene oxide: Z-scheme photocatalysis system for accelerated photocatalytic water disinfection, Appl. Catal. B: Environ., 218 (2017) 163–173. https://doi.org/10.1016/j.apcatb.2017.06.055
Kukushkin RG, Yeletsky PM, Grassin CT, Chen B H, et al., Deoxygenation of esters over sulfur-free Ni–W/Al2O3 catalysts for production of biofuel components, Chem. Eng. J., 396 (2020) 125202. https://doi.org/10.1016/j.cej.2020.125202
Matsuki N, Yao H, Water-dispersible black TiO2 nanodots doped with tungsten: Synthesis and distinctive optical transitions probed by MCD spectroscopy, J. Photochem. Photobiol. A: Chem., 478 (2026) 117146. https://doi.org/10.1016/j.jphotochem.2026.117146
Burdovitsin V, Dvilis E, Zenin A, Klimov A, et al., Electron beam sintering of zirconia ceramics, Adv. Mat. Res., 872 (2014) 150–156. https://doi.org/10.4028/www.scientific.net/AMR.872.150
Sigl M, Lutzmann S, Zaeh MF. Transient Physical Effects in Electron Beam Sintering. In: Proceedings for the 2006 International Solid Freeform Fabrication Symposium. The University of Texas at Austin: Austin; 2006. pp. 464–477. https://doi.org/10.26153/tsw/7154
Choi YM, Lee YL, Lim ES, Trimzi MA, et al., Performance improvement of ring-type PZT ceramics for ultrasonic dispersion system. Micromachines, 11(2) (2020) 144. https://doi.org/10.3390/mi11020144
Wang W, Ma S, Fuh JYH, Lu L, et al., Processing and characterization of laser-sintered Al2O3/ZrO2/SiO2, Int. J. Adv. Manuf. Technol., 68(9–12) (2013) 2565–2569. https://doi.org/10.1007/s00170-013-4863-7
Choi Y, Kim HW, Youn Y, Chun PJ, et al., Microwave-assisted sintering of a hexagonal perovskite-related protonic ceramic Ba7Nb4MoO20, J. Eur. Ceram. Soc., 44(14) (2024) 116702. https://doi.org/10.1016/j.jeurceramsoc.2024.116702
Kang H, Sowade E, Baumann RR, Photonic sintering of inkjet printed copper oxide layer, NIP & Digit. Fabr. Conf., 29 (2013) art00056_2. https://doi.org/10.2352/ISSN.2169-4451.2013.29.1.art00056_2
Fiuza TER, Focassio B, Bettini J, Schleder GR, et al., Visualization of electron beam-induced desintering of nanostructured ceramics at the atomic scale, Cell Rep. Phys. Sci., 5(2) (2024) 101828. https://doi.org/10.1016/j.xcrp.2024.101828
Yan J, Wang X, Chen K, Lee KN, Sintering modeling of thermal barrier coatings at elevated temperatures: A review of recent advances, Coatings, 11(10) (2021) 1214. https://doi.org/10.3390/coatings11101214
Tsao CY, Tuan WH, Feng KC, De-sintering of Ba5Nb4O15 ceramic and its influence on microwave characteristics, J. Eur. Ceram. Soc., 37(4) (2017) 1517–1521. https://doi.org/10.1016/j.jeurceramsoc.2016.11.002
Spierings AB, Schneider M, Eggenberger R, Comparison of density measurement techniques for additive manufactured metallic parts, Rapid Prototyp. J., 17(5) (2011) 380–386. https://doi.org/10.1108/13552541111156504
Ledwaba T, Mbuyisa B, Blakey-Milner B, Steenkamp C, et al., X-ray computed tomography vs Archimedes method: A head-to-head comparison, MATEC Web Conf., 388 (2023) 08002. https://doi.org/10.1051/matecconf/202338808002
Westphal1 E, Seitz H, Porosity and density measurement of additively manufactured components: A comparative analysis of measurement methods across processes and materials, Mater. Sci. Addit. Manuf., 4(2) (2025) 025090010. https://doi.org/10.36922/MSAM025090010
Fan K, Jiang W, Ruiz-Hervias J, Baudín C, et al., Effect of Al2TiO5 content and sintering temperature on the microstructure and residual stress of Al2O3–Al2TiO5 ceramic composites, Materials, 14(24) (2021) 7624. https://doi.org/10.3390/ma14247624
Løken A, Ricote S, Wachowski S, Thermal and chemical expansion in proton ceramic electrolytes and compatible electrodes, Crystals, 8(9) (2018) 365. https://doi.org/10.3390/cryst8090365
Escolástico S, Vert VB, Serra JM, Preparation and characterization of nanocrystalline mixed proton−electronic conducting materials based on the system Ln6WO12, Chem. Mater., 21(14) (2009) 3079–3089. https://doi.org/10.1021/cm900067k
Magrasó A, Hervoches CH, Ahmed I, Hull S, et al., In situ high temperature powder neutron diffraction study of undoped and Ca-doped La28−xW4+xO54+3x/2 (x = 0.85), J. Mater. Chem. A, 1(11) (2013) 3774–3782. https://doi.org/10.1039/c3ta00497j
Quarez E, Kravchyk KV, Joubert O, Compatibility of proton conducting La6WO12 electrolyte with standard cathode materials, Solid State Ionics, 216 (2012) 19–24. https://doi.org/10.1016/j.ssi.2011.11.003
López-Vergara A, Porras-Vázquez JM, Infantes-Molina A, Canales-Vázquez J, et al., Effect of preparation conditions on the polymorphism and transport properties of La6–xMoO12−δ (0 ≤ x ≤ 0.8), Chem. Mater., 29(16) (2017) 6966–6975. https://doi.org/10.1021/acs.chemmater.7b02481
Srivastava SP, Srivastava RC, Singh ID, Pandey SD, et al., Temperature dependence of thermal expansion and infrared lattice vibrational mode of nickel oxide, J. Phys. Soc. Jpn., 43(3) (1977) 885–890. https://doi.org/10.1143/JPSJ.43.885
Krynetskiĭ IB, Gizhevskiĭ BA, Naumov SV, Kozlov EA, Size effect of the thermal expansion of nanostructural copper oxide, Phys. Solid State, 50(4) (2008) 756–758. https://doi.org/10.1134/S1063783408040264
Sanson A, Rocca F, Dalba G, Fornasini P, et al., Negative thermal expansion and local dynamics in Cu2O and Ag2O, Phys. Rev. B, 73(21) (2006) 214305. https://doi.org/10.1103/PhysRevB.73.214305
Alex C, Shukla G, John NS, Introduction of surface defects in NiO with effective removal of adsorbed catalyst poisons for improved electrochemical urea oxidation, Electrochim. Acta, 385 (2021) 138425. https://doi.org/10.1016/j.electacta.2021.138425
Buckett MI, Marks LD, Electron irradiation damage in NiO, Surf. Sci., 232(3) (1990) 353–366. https://doi.org/10.1016/0039-6028(90)90129-v
Patel MA, Bhanvase BA, Sonawane SH, Production of cerium zinc molybdate nano pigment by innovative ultrasound assisted approach, Ultrason. Sonochem., 20(3) (2013) 906–913. https://doi.org/10.1016/j.ultsonch.2012.11.008
Colomban P, Proton and protonic species: The hidden face of solid state chemistry. How to measure H-content in materials?, Fuel Cells, 13(1) (2013) 6–18. https://doi.org/10.1002/fuce.201200088
Shlyakhtina AV, Pigalskiy KS, Belov DA, Lyskov NV, et al., Proton and oxygen ion conductivity in the pyrochlore/fluorite family of Ln2−xCaxScMO7−δ (Ln = La, Sm, Ho, Yb; M = Nb, Ta; x = 0, 0.05, 0.1) niobates and tantalates, Dalton Trans., 47(7) (2018) 2376–2392. https://doi.org/10.1039/c7dt03912c
Partin GS, Korona DV, Neiman AYa, Belova KG, Conductivity and hydration of fluorite-type La6−xWO12−1.5x phases (x = 0.4; 0.6; 0.8; 1), Russ. J. Electrochem., 51(5) (2015) 381–390. https://doi.org/10.1134/S1023193515050092
Niu J, Pan Z, Zhang K, Nanoconfined water in carbon capture and storage, Acad. Nano: Sci. Mater. Technol., 3(1) (2026). https://www.doi.org/10.20935/AcadNano8073
Haugsrud R, High temperature proton conductors – Fundamentals and functionalities, Diffus. Found., 8 (2016) 31–79. https://doi.org/10.4028/www.scientific.net/DF.8.31
Han D, Hatada N, Uda T, Chemical expansion of yttrium-doped barium zirconate and correlation with proton concentration and conductivity, J. Am. Ceram. Soc., 99(11) (2016) 3745–3753. https://doi.org/10.1111/jace.14377
Hancke R, Magrasó A, Norby T, Haugsrud R, Hydration of lanthanum tungstate (La/W = 5.6 and 5.3) studied by TG and simultaneous TG–DSC, Solid State Ionics, 231 (2013) 25–29.
Mogensen M, Lybye D, Bonanos N, Hendriksen PV, et al., Factors controlling the oxide ion conductivity of fluorite and perovskite structured oxides, Solid State Ionics, 174(1–4) (2004) 279–286. https://doi.org/10.1016/j.ssi.2004.07.036
Porras-Vázquez JM, dos Santos-Gómez L, Marrero-López D, Slater PR, et al., Effect of tri- and tetravalent metal doping on the electrochemical properties of lanthanum tungstate proton conductors, Dalton Trans., 45(7) (2016) 3130–3138. https://doi.org/10.1039/c5dt03833b
Steele BCH, Materials for IT-SOFC stacks: 35 years R&D: The inevitability of gradualness?, Solid State Ionics, 134(1–2) (2000) 3–20. https://doi.org/10.1016/S0167-2738(00)00709-8
Kazlauskas S. Charge Carrier Relaxation in Fluorite-Structured Oxygen Ion Conductors [dissertation]. Vilnius (Lithuania): Vilnius University; 2015. 107 p.
Hancke R, Fearn S, Kilner JA, Haugsrud R, Determination of proton- and oxide ion tracer diffusion in lanthanum tungstate (La/W = 5.6) by means of ToF-SIMS, Phys. Chem. Chem. Phys., 14(40) (2012) 13971–13978. https://doi.org/10.1039/c2cp42278f
Kopras P, Tsanaktsidis C, Kiratzis N, Advanced ceramic materials for electrolytes and electrodes in reversible solid oxide cells, Acad. Green Energy, 1(3) (2024). https://doi.org/10.20935/AcadEnergy7390
Chroneos A, Oxygen self-diffusion in fluorite high entropy oxides, Appl. Sci., 14(12) (2024) 5309. https://doi.org/10.3390/app14125309
De Souza RA, Kilner JA, Jeynes C, The application of secondary ion mass spectrometry (SIMS) to the study of high temperature proton conductors (HTPC), Solid State Ionics, 97(1–4) (1997) 409–419. https://doi.org/10.1016/S0167-2738(97)00038-6
Kalland LEQ. Ab Initio Modelling and Experimental Studies of Order-Disorder, Hydration, and Ionic Conductivity of Fluorite Related Oxides [dissertation]. Oslo (Norway): University of Oslo; 2020. 123 p.
Ming J, Leszczyńska-Redek M, Malys M, Wrobel W, et al., Dopant clustering and vacancy ordering in neodymium doped ceria, J. Mater. Chem. A, 12(17) (2024) 10203–10215. https://doi.org/10.1039/d3ta07668g
Ming J, Zhang X, Leszczyńska-Redek M, Malys M, et al., Probing dopant size effects on defect clustering and vacancy ordering in lanthanide-doped ceria, J. Am. Chem. Soc., 147(35) (2025) 31992–32004. https://doi.org/10.1021/jacs.5c09862
Sickafus K, Grimes R, Valdez J, Cleave A, et al., Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides, Nature Mater., 6 (2007) 217–223. https://doi.org/10.1038/nmat1842
Pasagada VKV, Yang N, Xu C, Electron beam sintering (EBS) process for ultra-high temperature ceramics (UHTCs) and the comparison with traditional UHTC sintering and metal electron beam melting (EBM) processes, Ceram. Int., 48(7) (2022) 10174–10186. https://doi.org/10.1016/j.ceramint.2021.12.229
Rushton MJD, Stanek CR, Cleave AR, Uberuaga BP, et al., Simulation of defects and defect processes in fluorite and fluorite related oxides: Implications for radiation tolerance, Nucl. Instrum. Methods Phys. Res. B: Beam Interact. Mater. At., 255(1) (2007) 151–157. https://doi.org/10.1016/j.nimb.2006.11.018
Eremeev N, Sadovskaya E, Bespalko Yu, Smal E, et al., Oxygen mobility and surface reactivity of Sm-doped Pr nickelates as promising materials for solid oxide cell air electrodes, Chim. Tech. Acta, 13(4) (2026) 10130. https://doi.org/10.15826/chimtech.10130
Turcotte RP, Redox behavior and phase stability in binary, ternary, and high-entropy oxide solid solutions, Acad. Mater. Sci., 3(1) (2026). https://www.doi.org/10.20935/AcadMatSci8135
Sadykov VA, Sadovskaya EM, Eremeev NF, Skriabin PI, et al., Oxygen mobility in the materials for solid oxide fuel cells and catalytic membranes (Review), Russ. J. Electrochem., 55(8) (2019) 701–718. https://doi.org/10.1134/S1023193519080147
Sadykov VA, Bespalko YuN, Krasnov AV, Skriabin PI, et al., Novel proton-conducting nanocomposites for hydrogen separation membranes, Solid State Ionics, 322 (2018) 69–78. https://doi.org/10.1016/j.ssi.2018.05.003
Kim HJ, Lee SH, Kim SH, Lee SG, et al., Effects of the sintering temperature on the properties of Ce0.85Gd0.1Ca0.05O2−δ electrolyte materials for SOFC, Integr. Ferroelectr., 140(1) (2012) 71–76. https://doi.org/10.1080/10584587.2012.741453
Choudhary B, Anwar S, Medvedev DA, Besra L, et al., Effect of sintering temperature on the transport properties of La2Ce2O7 ceramic materials, Ceram. Int., 48(5) (2022) 6758–6766. https://doi.org/10.1016/j.ceramint.2021.11.227
Moreno KJ, Fuentes AF, Maczka M, Hanuza J, et al., Influence of thermally induced oxygen order on mobile ion dynamics in Gd2(Ti0.65Zr0.35)2O7, Phys. Rev. B, 75(18) (2007) 184303. https://doi.org/10.1103/PhysRevB.75.184303
Wachsman ED, Boyapati S, Kaufman MJ, Jiang N, Modeling of ordered structures of phase-stabilized cubic bismuth oxides, J. Am. Ceram. Soc., 83(8) (2000) 1964–1968. https://doi.org/10.1111/j.1151-2916.2000.tb01498.x
Li Q, Thangadurai V, Synthesis, structure and electrical properties of Mo-doped CeO2 – materials for SOFCs, Fuel Cells, 9(5) (2009) 684–698. https://doi.org/10.1002/fuce.200900044
Johnston-Peck AC, DuChene JS, Roberts AD, Wei WD, et al., Dose-rate-dependent damage of cerium dioxide in the scanning transmission electron microscope, Ultramicroscopy, 170 (2016) 1–9. https://doi.org/10.1016/j.ultramic.2016.07.002
Šiška Z, Sojková T, Sojka M, Roupcová P, et al., Microtron electron beam enables post-synthetic defect engineering in ultrasmall ceria nanocrystals, Nanoscale Adv., 8(13) (2026) 3666–3679. https://doi.org/10.1039/d6na00191b
Sadykov V, Shlyakhtina A, Sadovskaya E, Eremeev N, et al., 2D diffusion of oxygen in Ln10Mo2O21 (Ln = Nd, Ho) oxides, Solid State Ionics, 346 (2020) 115229. https://doi.org/10.1016/j.ssi.2020.115229
Wang X, Zhang H, Baba T, Jiang H, et al., Radiation-induced segregation in a ceramic, Nat. Mater., 19 (2020) 992–998. https://doi.org/10.1038/s41563-020-0683-y
Symington AR, Molinari M, Brincat NA, Williams NR, et al., Defect segregation facilitates oxygen transport at fluorite UO2 grain boundaries, Phil. Trans. R. Soc. A, 377(2152) (2019) 20190026. https://doi.org/10.1098/rsta.2019.0026
Sadykov VA, Sadovskaya EM, Bespalko YuN, Smal’ EA, et al., Structural, surface and oxygen transport properties of Sm-doped Nd nickelates, Solid State Ionics, 412 (2024) 116596. https://doi.org/10.1016/j.ssi.2024.116596
Sadykov VA, Sadovskaya EM, Bespalko YuN, Smal’ EA, et al., Oxygen mobility of samarium doped neodymium nickelates sintered by e-beams, Russ. J. Electrochem., 61(2) (2025) 28–39. https://doi.org/10.1134/S1023193524601670
Farlenkov AS, Ananyev MV, Eremin VA, Porotnikova NM, et al., Oxygen isotope exchange in doped calcium and barium zirconates, Solid State Ionics, 290 (2016) 108–115. https://doi.org/10.1016/j.ssi.2016.04.015
Kreuer KD, Dippel Th, Baikov YuM, Maier J, Water solubility, proton and oxygen diffusion in acceptor doped BaCeO3: A single crystal analysis, Solid State Ionics, 86–88(1) (1996) 613–620. https://doi.org/10.1016/0167-2738(96)00221-4
Farlenkov AS, Putilov LP, Ananyev MV, Antonova EP, et al., Water uptake, ionic and hole transport in La0.9Sr0.1ScO3−δ, Solid State Ionics, 306 (2017) 126–136. https://doi.org/10.1016/j.ssi.2017.04.013
Farlenkov AS, Khodimchuk AV, Shevyrev NA, Stroeva AYu, et al., Oxygen isotope exchange in proton-conducting oxides based on lanthanum scandates, Int. J. Hydrogen Energy, 44(48) (2019) 26577–26588. https://doi.org/10.1016/j.ijhydene.2019.08.088
Altynbekova D, Bespalko Yu, Valeev K, Eremeev N, et al., Simple approach to the fabrication of lanthanum orthoniobates and nanocomposites with Ni, Cu, and Co metal nanoparticles using supercritical isopropanol, J. Compos. Sci., 6(9) (2022) 243. https://doi.org/10.3390/jcs6090243
Packer RJ, Tsipis EV, Munnings CN, Kharton VV, et al., Diffusion and conductivity properties of cerium niobate, Solid State Ionics, 177(19–25) (2006) 2059–2064. https://doi.org/10.1016/j.ssi.2006.03.044
DOI: https://doi.org/10.15826/elmattech.2026.5.077
Copyright (c) 2026 Nikita F. Eremeev, Ekaterina M. Sadovskaya, Tamara A. Krieger, Olga A. Bulavchenko, Vasily V. Kaichev, Anna M. Kremneva, Evgeny A. Suprun, Mostefe Khalid Mohammed, Mikhail A. Mikhailenko, Mikhail V. Korobeynikov, Vladislav A. Sadykov, Yulia N. Bespalko
This work is licensed under a Creative Commons Attribution 4.0 International License.
