研究者データベース

研究者情報

マスター

アカウント(マスター)

  • 氏名

    NATALY CAROLINA ROSERO NAVARRO(ナタリー カロリーナ ロゼロ ナバロ), ナタリー カロリーナ ロゼロ ナバロ

所属(マスター)

  • 工学研究院 応用化学部門 無機材料化学分野

所属(マスター)

  • 工学研究院 応用化学部門 無機材料化学分野

独自項目

syllabus

  • 2020, 応用化学特別講義, Advanced-Applied Chemistry, 修士課程, 総合化学院, energy conversion devices, energy storage devices, solar cells, all nano-structures, solid state batteries
  • 2020, 先端総合化学特論Ⅱ, Modern Trends in Chemical Sciences and Engineering II, 博士後期課程, 総合化学院, energy conversion devices, energy storage devices, solar cells, all nano-structures, solid state batteries
  • 2020, 国際交流Ⅰ, Arts and Science Courses in English 1, 学士課程, 国際本部, advanced inorganic materials, ceramics, glasses, applications
  • 2020, 工学特別講義, Special Lecture on Engineering, 学士課程, 工学部, energy conversion devices, energy storage devices, solar cells, all nano-structures, solid state batteries
  • 2020, 化学英語, English for Chemistry, 学士課程, 工学部, 化学,英語,単語,表記法
  • 2020, 応用化学学生実験Ⅱ, Applied Chemistry Laboratory Ⅱ, 学士課程, 工学部, 固相反応、焼結、固溶体、X線回折、電子顕微鏡、熱分析、セラミックス

researchmap

プロフィール情報

プロフィール情報

  • ロゼロ
  • カロリーナ
  • ID各種

    201601020396153313

業績リスト

研究キーワード

  • Hybrid Materials Science   Electrochemistry   Inorganic Materials Science   

研究分野

  • ナノテク・材料 / 無機材料、物性

経歴

  • 2016年10月 - 現在 Hokkaido University Assistant Professor
  • 2015年11月 - 2016年09月 Hokkaido University Postdoctoral Researcher
  • 2013年11月 - 2015年11月 Hokkaido University JSPS Postdoctoral Fellow
  • 2012年05月 - 2013年10月 University of Aveiro (Portugal) FCT Postdoctoral Fellow
  • 2011年09月 - 2012年04月 Institute of Materials Science of Seville (Spain) Research Contract
  • 2005年05月 - 2011年08月 Institute of Ceramic and Glass (Spain) Research Contract/PhD JAE-CSIC Fellowship

学歴

  • 2007年10月 - 2011年06月   University Autonoma of Madrid   PhD Degree
  • 2005年09月 - 2007年09月   University Autonoma of Madrid   DEA Degree

論文

  • Nataly Carolina Rosero-Navarro, Haruna Watanabe, Akira Miura, Kiyoharu Tadanaga
    Journal of the European Ceramic Society 41 13 6767 - 6771 2021年10月 [査読有り]
  • Marcela Calpa, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
    Journal of Sol-Gel Science and Technology 2021年09月16日 [査読有り]
  • Shinji Noguchi, Jin Odahara, Hayato Sakai, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
    Inorganic Chemistry 60 17 12753 - 12758 2021年09月06日 [査読有り]
  • Hiroaki Ito, Kazuki Shitara, Yongming Wang, Kotaro Fujii, Masatomo Yashima, Yosuke Goto, Chikako Moriyoshi, Nataly Carolina Rosero‐Navarro, Akira Miura, Kiyoharu Tadanaga
    Advanced Science 8 15 2101413 - 2101413 2021年08月 [査読有り]
  • A. Miura, C.J. Bartel, Y. Goto, Y. Mizuguchi, C. Moriyoshi, Y. Kuroiwa, Y. Wang, T. Yaguchi, M. Shirai, M. Nagao, N.C. Rosero-Navarro, K. Tadanaga, G. Ceder, W. Sun
    Advanced Materials 2100312 - 2100312 2021年05月 [査読有り]
  • Hiroki ITO, Akira MIURA, Yosuke GOTO, Yoshikazu MIZUGUCHI, Chikako MORIYOSHI, Yoshihiro KUROIWA, Nataly Carolina ROSERO-NAVARRO, Kiyoharu TADANAGA
    Journal of the Ceramic Society of Japan 129 5 249 - 253 2021年05月01日 [査読有り]
     
    The magnetic and electronic properties of CeOInS and their influence on phase transition were analyzed in this study. High-temperature XRD measurements of CeOInS revealed that orthorhombic CeOInS transformed into tetragonal CeOInS at a high temperature of 636 K. The transport properties of CeOInS showed semiconducting behavior, with a larger temperature dependence of electronic resistivity in the tetragonal phase compared to that in the orthorhombic phase. Unlike structurally similar Ce(O,F)BiS superconductors that show long-range magnetic ordering, CeOInS neither exhibited superconductive transition nor long-range magnetic ordering at temperatures between 2 and 300 K. 2 2 2 2 2 2 2
  • Marcela Calpa, Hiroshi Nakajima, Shigeo Mori, Yosuke Goto, Yoshikazu Mizuguchi, Chikako Moriyoshi, Yoshihiro Kuroiwa, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
    Inorganic Chemistry 2021年04月29日 [査読有り]
  • Yuta Fujii, Hiroaki Ito, Akira Miura, Nataly Carolina Rosero-Navarro, Kiyoharu Tadanaga, Li Lu
    Functional Materials Letters 2141005 - 2141005 2021年03月18日 [査読有り]
     
    We report the fast discharge–charge cycle of micro-sized FePS3 electrode particles in all-solid-state batteries (ASSBs) using sulfide electrolytes at 80[Formula: see text]C. At a current density of 2.04 mA cm[Formula: see text], corresponding to approximately 1 C, the capacity of the FePS3 electrodes reached [Formula: see text]180 mAh g[Formula: see text] without any electron or lithium-ion conductive additives. Galvanostatic intermittent titration technique (GITT) measurements showed a stable diffusion path of FePS3 represented by the product of the diffusion coefficient and square of the surface area. These electrochemical properties were compared with those of FeS, whose capacity was lower because of its unstable diffusion path.
  • F. A. Vásquez, N. C. Rosero-Navarro, A. Miura, R. Jalem, Y. Goto, M. Nagao, Y. Tateyama, K. Tadanaga, J. A. Calderón
    ACS Applied Materials & Interfaces 2021年03月16日 [査読有り]
  • Marcela Calpa, Nataly Carolina Rosero-Navarro, Akira Miura, Randy Jalem, Yoshitaka Tateyama, Kiyoharu Tadanaga
    Applied Materials Today 22 100918 - 100918 2021年03月 [査読有り]
     
    Sulfide solid electrolytes in the Li PS –LiI system are promising for all-solid-state batteries owing to their high ionic conductivity in the order of 10 S cm and electrochemical stability. Nonetheless, the low chemical stability tendency of sulfide-based materials under ambient atmosphere is a critical issue due to the generation of toxic H S gas. In this study, the chemical stability of Li PS I (Li PS –LiI) solid electrolyte under ambient atmosphere was investigated and compared with that of Li PS to analyze the effect of the incorporation of LiI on the chemical stability of sulfide-based electrolytes. No generation of H S gas was detected in the Li PS I solid electrolyte after an exposure of 60 min to the ambient atmosphere with high relative humidity of 40%. The hydrolysis suppression is attributed to the formation of LiI·H O, acting as a protective barrier between PS units in the electrolyte and H O molecules in air. The structural reversibility of Li PS I by simple drying at 180°C was confirmed and the solid electrolyte exhibited an ionic conductivity of 10 S cm at room temperature, similar to that of the sample before the exposure to the ambient atmosphere. 3 4 2 4 4 3 4 3 4 2 4 4 2 4 2 4 4 −4 −1 3− −4 −1
  • Kiyoharu Tadanaga, Nataly Carolina Rosero-Navarro, Akira Miura
    Next Generation Batteries 85 - 92 2021年
  • Riku Maniwa, Marcela Calpa, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
    Journal of Materials Chemistry A 9 1 400 - 405 2021年 [査読有り]
     

    We report the liquid-phase synthesis of sulfide solid electrolytes from Li2S and P2S5 using anisole at 200–300 °C under microwave irradiation, in which β-Li3PS4 and Li7P3S11 were directly precipitated in anisole in 30 min.

  • Marcela Calpa, Nataly Carolina Rosero-Navarro, Akira Miura, Kota Terai, Futoshi Utsuno, Kiyoharu Tadanaga
    Chemistry of Materials 32 22 9627 - 9632 2020年11月24日 [査読有り]
  • Nataly Carolina Rosero-Navarro, Ryunosuke Kajiura, Akira Miura, Kiyoharu Tadanaga
    ACS Applied Energy Materials 3 11 11260 - 11268 2020年11月23日 [査読有り]
  • Akira MIURA, Sho ISHIYAMA, Daiju KUBO, Nataly Carolina ROSERO-NAVARRO, Kiyoharu TADANAGA
    Journal of the Ceramic Society of Japan 128 7 336 - 339 2020年07月01日 [査読有り]
  • Nataly Carolina Rosero-Navarro, Ryunosuke Kajiura, Randy Jalem, Yoshitaka Tateyama, Akira Miura, Kiyoharu Tadanaga
    ACS Applied Energy Materials 3 6 5533 - 5541 2020年06月22日 [査読有り]
  • Electrical properties of Pyrochlore-type Silver Tantalate and Fluorite-type Silver Niobate
    W.Isuru, U. Withanage, N. Kumada, T. Takei, K. Tadanaga A. Miura, N.C. Rosero-Navarro, M. Azuma.
    Journal of the Ceramic Society of Japan 128 788 - 792 2020年 [査読有り][通常論文]
  • Selective metathesis synthesis of MgCr2S4 by control of thermodynamic driving forces
    A. Miura, H. Ito, C. J. Bartel, W. Sun, N.C. Rosero-Navarro, K. Tadanaga, H. Nakata, K. Maeda, G. Ceder.
    Materials Horizon 2020年 [査読有り][通常論文]
  • Y. Fujii, M. Kobayashi, A. Miura, N.C. Rosero-Navarro, M. Li, J. Sun, M. Kotobuki, L. Lu, K. Tadanaga
    Journal of Power Sources 449 227576  2020年 [査読有り][通常論文]
  • Enhanced hydroxide ion conductivity of Mg-Al layered double hydroxide at low humidity by intercalating dodecyl sulfate anion
    Kubo, D, Igarashi, K, Ishiyama, S, Rosero Navarro, N.C, Miura, A, Higuchi, M, Tadanaga, K
    J. Ceram. Soc. Jpn. 127 11 788 - 792 2019年11月 [査読有り][通常論文]
  • Y. Fujii, D. Ramirez, N.C. Rosero-Navarro, J. Domingo, A. Miura, F. Jaramillo, K. Tadanaga
    ACS Applied Energy Materials 2019年08月 [査読有り][通常論文]
  • S. Ishiyama, N. C. Rosero-Navarro, A. Miura, K. Tadanaga
    Materials Research Bulletin 119 110561  2019年07月 [査読有り][通常論文]
  • H. Ito, A. Miura, Yosuke Goto, Yoshikazu Mizuguchi, Chikako Moriyoshi, Yoshihiro Kuroiwa, Masaki Azuma, Jinjia Liu, Xiao-Dong Wen, Shunta Nishioka, Kazuhiko Maeda, Yuji Masubuchi, N.C. Rosero-Navarro, K. Tadanaga
    Dalton Transactions 48 32 12272 - 12278 2019年07月 [査読有り][通常論文]
     
    An extremely large displacement of the indium site in In-S-6 octahedra in LnOInS(2) (Ln = La, Ce, and Pr) was found in synchrotron X-ray diffraction. LaOInS2 with off-center indium in In-S-6 octahedra exhibited a wider optical band gap than CeOInS2 and PrOInS2 with on-center indium. Therefore, the electronic structure of LnOInS(2) is governed by the indium site with an extremely large displacement. All LnOInS(2) produced H-2 gas under visible light irradiation in the presence of sacrificial electron donors.
  • Lyn Marie, Z. De Juan-Corpuz, Mai Thanh Nguyen, Ryan D. Corpuz, Tetsu Yonezawa, Nataly Carolina Rosero-Navarro, Kiyoharu Tadanaga, Tomoharu Tokunaga, Soorathep Kheawhom
    ACS Applied Nano Materials 2 7 4247 - 4256 2019年06月 [査読有り][通常論文]
  • Odahara, Jin, Sun, Wenhao, Miura, Akira, Rosero-Navarro, Nataly Carolina, Masanori, Nagao, Isao, Tanaka, Ceder, Gerbrand, Tadanaga, Kiyoharu
    ACS Materials Letters 1 64 - 70 2019年05月 [査読有り][通常論文]
  • Yu Iwai, Takuya Ikka, A. Miura, N.C. Rosero-Navarro, Shinichiroh Iwamura, Isao Ogino, Shin R. Mukai, K. Tadanaga
    Chemistry Letters 48 7 696 - 699 2019年04月 [査読有り][通常論文]
  • Miura, Akira, Rosero-Navarro, Nataly Carolina, Sakuda, Atsushi, Tadanaga, Kiyoharu, Phuc, Nguyen H. H, Matsuda, Atsunori, Machida, Nobuya, Hayashi, Akitoshi, Tatsumisago, Masahiro
    Nature Reviews Chemistry 3 189 - 193 2019年03月 [査読有り][招待有り]
  • Iwai, Yu, Miura, Akira, Rosero-Navarro, Nataly Carolina, Higuchi, Mikio, Tadanaga, Kiyoharu
    Journal of Asian Ceramic Societies 7 2 147 - 153 2019年02月 [査読有り][通常論文]
  • M.Calpa, N.C. Rosero-Navarro, A. Miura, K. Tadanaga
    Electrochimica Acta 296 473 - 480 2019年02月 [査読有り][通常論文]
  • Ionic conductivity of Pyrochlore-type Silver Tantalate and Fluorite-type Silver Niobate
    W. I, U. WITHANAGE, Nobuhiro Kumada, Takahiro Takei, Sayaka YANAGIDA, Kiyoharu Tadanaga, Akira Miuram Nataly Carolina Rosero-Navarro, Masaki Azuma
    J. Ceram. Soc. Jpn. in press 2019年 [査読有り][通常論文]
  • G.V. Alexander, N.C. Rosero-Navarro, A. Miura, K. Tadanaga, R. Murugan
    Journal of Material Chemistry A 2018年10月 [査読有り][通常論文]
  • Y. Fujii, A. Miura, N.C. Rosero-Navarro, Y. Mizuguchi, Y. Kuroiwa, C. Moriyoshi, M. Higuchi, K. Tadanaga
    Journal of The Electrochemical Society 165 13 A2948 - A2954 2018年09月 [査読有り][通常論文]
  • Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
    Journal of Power Sources 396 33 - 40 2018年08月31日 [査読有り][通常論文]
     
    All-solid-state lithium batteries based on sulfide solid electrolytes are potential candidates for large-scale energy storage applications. Here, composite cathode with high content of an active material was prepared by a liquid phase process assisted by a dispersant agent to produce a better electrode and electrolyte interface. Li6PS5Cl sulfide electrolyte derived from a solution containing dispersant showed an argyrodite crystal phase with a better distribution of particle size and higher conductivity compared with those without dispersant. Regular distribution of Li6PS5Cl particles in nanometric scale with a spherical shape below 500 nm and conductivity of 0.6 × 10−3 S cm−1 (ρ = 1.40 g cm−3) at room temperature were obtained. Composite cathode was prepared by the dispersion of LiNi1/3Mn1/3Co1/3O2 particles and carbon additive in the Li6PS5Cl-solution containing dispersant agent and subsequent drying at 180 °C. Bulk-type all-solid-state battery fabricated with the composite cathode containing 89 wt% of the active material showed an initial discharge capacity of 110 mA h g−1 at 25 °C and maintained 95% discharge capacity after 15 cycles.
  • Akira Miura, Masanori Nagao, Yosuke Goto, Yoshikazu Mizuguchi, Tatsuma D. Matsuda, Yuji Aoki, Chikako Moriyoshi, Yoshihiro Kuroiwa, Yoshihiko Takano, Satoshi Watauchi, Isao Tanaka, Nataly Carolina Rosero-Navarro, Kiyoharu Tadanaga
    Inorganic Chemistry 57 9 5364 - 5370 2018年05月07日 [査読有り][通常論文]
     
    Ce1-xPrxOBiS2 powders and Ce0.5Pr0.5OBiS2 single crystals were synthesized and their structure and superconductive properties were examined by X-ray diffraction, X-ray absorption, electronic resistivity, and magnetization. While PrOBiS2 was found to be in a monoclinic phase with one-dimensional Bi-S zigzag chains showing no superconductive transition above 0.1 K, CeOBiS2 was in a tetragonal phase with two-dimensional Bi-S planes showing zero resistivity below 1.3 K. In the range x = 0.3-0.9 in Ce1-xPrxOBiS2, both monoclinic and tetragonal phases were formed together with zero resistivity up to a maximum temperature of 2.2 K. A Ce0.5Pr0.5OBiS2 single crystal, which showed both zero resistivity and a decrease in magnetization at ∼2.4 K, presented a tetragonal structure. Short Bi-S bonding in flat two-dimensional Bi-S planes and mixed Ce3+/Ce4+ were characteristic features of the Ce0.5Pr0.5OBiS2 single crystal, which presumably triggered its superconductivity.
  • Daniel Ramirez, Yusaku Suto, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga, Franklin Jaramillo
    Inorganic Chemistry 57 7 4181 - 4188 2018年04月02日 [査読有り][通常論文]
     
    Organic-inorganic hybrid perovskite materials have recently been investigated in a variety of applications, including solar cells, light emitting devices (LEDs), and lasers because of their impressive semiconductor properties. Nevertheless, the perovskite structure has the ability to host extrinsic elements, making its application in the battery field possible. During the present study, we fabricated and investigated the electrochemical properties of three-dimensional (3D) methylammonium lead mixed-halide CH3NH3PbI3-xBrx and two-dimensional (2D) propylammonium-methlylammonium lead bromide (CH3NH3)2(CH3(CH2)2NH3)2Pb3Br10 hybrid perovskite thin films as electrode materials for Li-ion batteries. These electrodes were obtained by solution processing at 100 °C. CH3NH3PbBr3 achieved high discharge/charge capacities of ∼500 mA h g-1 /160 mA h g-1 that could account also for other processes taking place during the Li intercalation. It was also found that bromine plays an important role for lithium intercalation, while the new 2D (CH3NH3)2(CH3(CH2)2NH3)2Pb3Br10 with a layered structure allowed reversibility of the lithium insertion-extraction of 100% with capacities of ∼375 mA h g-1 in the form of a thin film. Results suggest that tuning the composition of these materials can be used to improve intercalation capacities, while modification from 3D to 2D layered structures contributes to improving lithium extraction. The mechanism of the lithium insertion-extraction may consist of an intercalation mechanism in the hybrid material accompanying the alloying-dealloying process of the LixPb intermetallic compounds. This work contributes to revealing the relevance of both composition and structure of potential hybrid perovskite materials as future thin film electrode materials with high capacity and compositional versatility.
  • Jin Odahara, Akira Miura, Nataly Carolina Rosero-Navarro, Kiyoharu Tadanaga
    Inorganic Chemistry 57 1 24 - 27 2018年01月02日 [査読有り][通常論文]
     
    An intense exothermic and explosive reaction between Ba(OH)2, NbCl5, and NaNH2 produced barium niobium perovskite oxynitride in seconds. The addition of hexane reduced the risk of explosion during mixing of the starting materials, and subsequent heat treatment at 498 K in hexane allowed control of this exothermic reaction, leading to formation of the perovskite oxynitride with fewer impurities. The synthesis of barium tantalum perovskite oxynitride under similar reaction conditions was successful.
  • Synthesis of submicron-sized NiPS3 particles and electrochemical properties as active materials in all-solid-state lithium batteries
    Y. Suto, Y. Fujii, A. Miura, N.C. Rosero-Navarro, K. Tadanaga
    Journal of the Ceramics Society Japan 2018年 [査読有り][通常論文]
  • N.C. Rosero-Navarro, A. Miura, K. Tadanaga
    Journal of Sol-Gel Science and Technology 2018年 [査読有り][招待有り]
  • N. Takahashi, H. Ito, A. Miura, N.C. Rosero-Navarro, Y. Goto, Y. Mizuguchi, C. Moroyoshi, Y. Kuroiwa, M. Nagao, S. Watauchi, I. Tanaka, K. Tadanaga
    Journal of Alloys and Compounds 2018年 [査読有り][通常論文]
  • Shunjiro Chida, Akira Miura, Nataly Carolina Rosero-Navarro, Mikio Higuchi, Nguyen H. H. Phuc, Hiroyuki Muto, Atsunori Matsuda, Kiyoharu Tadanaga
    CERAMICS INTERNATIONAL 44 1 742 - 746 2018年01月 [査読有り][通常論文]
     
    Lithium-ion conductive Li6PS5Br is prepared using ultrasonication of Li2S, P2S5 and LiBr in ethyl propionate-ethanol solution and subsequent heating at 453 K. The main phase of the synthesized product is Li6PS5Br and its lithium ion conductivity is 3.4 x 10(-5) S cm(-1) at room temperature. The cathode composite of LiCo1/3Ni1/3Mn1/3O2, Li6PS5Br and vapor grown carbon fiber (VGCF) is prepared via ultrasonication of the Li6PS5Br precursor solution containing LiCo1/3Ni1/3Mn1/3O2 and VGCF, and the all-solid-state lithium battery using this cathode composite is fabricated. The cell exhibits the discharge capacity of 109 mAh g(-1) for the first cycle and its capacity of 87 mAh g(-1) after 10 cycles.
  • Yuta Fujii, Akira Miura, Nataly Carolina Rosero-Navarro, Mikio Higuchi, Kiyoharu Tadanaga
    ELECTROCHIMICA ACTA 241 370 - 374 2017年07月 [査読有り][通常論文]
     
    In bulk-type all-solid-state lithium batteries with sulfide-based solid electrolytes, composite electrodes, in which an active material, a solid electrolyte, and a conductive additive are mixed, have been used to enhance lithium-ion diffusion and electronic conductivity. However, the addition of electrolytes and electron-conductive additives to the composite electrodes decreases the amount of active materials in the batteries. In the present study, FePS3 was employed as the electrode in an all-solid-state lithium secondary battery, without mixing the solid electrolytes and conductive additives. The all-solid-state cell using the FePS3 electrode exhibited reversible charge-discharge behavior for more than 30 cycles under a constant current density of 0.13 mA cm (2) at room temperature. The discharge capacity of the cell was 107 mAh g (1) at the 30th cycle. This behavior was comparable to that of a cell with an electrode including a solid electrolyte and/or a conductive additive, indicating that the FePS3 electrode had sufficient paths of lithium ions and of electron conduction. These results suggest that FePS3 is an attractive iron-based electrode for an all-solid-state battery using a sulfide-based solid electrolyte. (C) 2017 Elsevier Ltd. All rights reserved.
  • Nataly Carolina Rosero-Navarro, Taiki Kinoshita, Akira Miura, Mikio Higuchi, Kiyoharu Tadanaga
    IONICS 23 6 1619 - 1624 2017年06月 [査読有り][通常論文]
     
    All-solid-state batteries with cathode composites containing high concentration of active materials are required to achieve higher energy densities. Here, a composite cathode containing up to 89 wt% of high-voltage cathode active material (LiNi1/3Mn1/3Co1/3O2) was prepared by covering this with a solution-derived solid electrolyte (argyrodite, Li6PS5Cl) and the incorporation of different content binder (ethyl cellulose). All-solid-state batteries were fabricated using 80Li(2)Sa (TM) 20P(2)S(5) (mol%) glass and indium metal as a solid electrolyte and anode, respectively. The all-solid-state battery with a composite cathode containing 0.5 wt% of ethyl cellulose showed an initial discharge capacity of 45 mAhg(-1) at 25 A degrees C and maintained 91.7% of the discharge capacity after ten cycles, around 30% higher than that obtained for the battery with the composite cathode without a binder.
  • Tiago D. O. Gadim, Francisco J. A. Loureiro, Carla Vilela, Nataly Rosero-Navarro, Armando J. D. Silvestre, Carmen S. R. Freire, Filipe M. L. Figueiredo
    ELECTROCHIMICA ACTA 233 52 - 61 2017年04月 [査読有り][通常論文]
     
    The effect of the preferential orientation of supporting bacterial cellulose (BC) nanofibrils on the conductivity of composite proton conducting electrolytes with poly(4-styrene sulfonic acid) (PSSA) is reported. Data obtained by impedance spectroscopy show that the in-plane conductivity at 40% relative humidity (RH) is more than half order of magnitude higher than that measured through-plane, indicating significant discontinuity of proton transport at the PSSA/BC interface. The difference becomes less than 20% in nearly saturated conditions (98% RH), demonstrating the key role of water in ensuring proton transport through those interfaces. The negative impact of the conductivity anisotropy in fuel cell performance is mitigated due to operation in wet conditions and fuel cell tests of PSSA/BC-based membrane electrode assemblies under humidified hydrogen/air gradients at room temperature yield 40 mW cm(-2) at 125 mA cm(-2), which is amongst the highest values reported for a biopolymer-based electrolyte. It also results from the presented investigation that conventional electrode preparation used for thermoplastic polymer electrolytes must be modified in order to ensure proper adhesion to BC-based MEAs and thus to lower polarization losses. (C) 2017 Elsevier Ltd. All rights reserved.
  • Marcela Calpa, Nataly Carolina Rosero-Navarro, Akira Miura, Kiyoharu Tadanaga
    RSC ADVANCES 7 73 46499 - 46504 2017年 [査読有り][通常論文]
     
    A solid electrolyte with a small particle size, good mechanical properties and high ionic conductivity is required to achieve high energy and power density in the all-solid-state battery. Here, we report an instantaneous preparation of high lithium-ion conducting sulfide solid electrolyte Li7P3S11 by a simple procedure involving a liquid phase process under ultrasonic irradiation and low thermal treatment at 220 degrees C. A short reaction time of 30 min was enough to produce the formation of PS43- units. Subsequent drying and heating processes led to the precipitation of the Li7P3S11 phase with a particle size below 500 nm, achieving high ionic conductivity of 1.0 x 10(-3) S cm(-1) at 22 degrees C and a low activation energy of 12.8 kJ mol(-1).
  • A. Miura, S. Ishii, M. Nagao, R. Matsumoto, Y. Takano, S. Watauchi, I. Tanaka, N. C. Rosero-Navarro, K. Tadanaga
    Journal of Asian Ceramic Societies 5 2 183 - 185 2017年 [査読有り][通常論文]
  • Nataly Carolina Rosero-Navarro, Taira Yamashita, Akira Miura, Mikio Higuchi, Kiyoharu Tadanaga
    JOURNAL OF THE AMERICAN CERAMIC SOCIETY 100 1 276 - 285 2017年01月 [査読有り][通常論文]
     
    Lithium ion conductors with garnet-type structure are promising candidates for applications in all solid-state lithium ion batteries, because these materials present a high chemical stability against Li metal and a rather high Li+ conductivity (10(-3)-10(-4)S/cm). Producing densified Li-ion conductors by lowering sintering temperature is an important issue, which can achieve high Li conductivity in garnet oxide by preventing the evaporation of lithium and a good Li-ion conduction in grain boundary between garnet oxides. In this study, we concentrate on the use of sintering additives to enhance densification and microstructure of Li7La3ZrNbO12 at sintering temperature of 900 degrees C. Glasses in the LiO2-B2O3-SiO2-CaO-Al2O3 (LBSCA) and BaO-B2O3-SiO2-CaO-Al2O3 (BBSCA) system with low softening temperature (<700 degrees C) were used to modify the grain-boundary resistance during sintering process. Lithium compounds with low melting point (<850 degrees C) such as LiF, Li2CO3, and LiOH were also studied to improve the rearrangement of grains during the initial and middle stages of sintering. Among these sintering additives, LBSCA and BBSCA were proved to be better sintering additives at reducing the porosity of the pellets and improving connectivity between the grains. Glass additives produced relative densities of 85-92%, whereas those of lithium compounds were 62-77%. Li7La3ZrNbO12 sintered with 4 wt% of LBSCA at 900 degrees C for 10h achieved a rather high relative density of 85% and total Li-ion conductivity of 0.8x10(-4)S/cm at room temperature (30 degrees C).
  • Akira Miura, Carolina Rosero-Navarro, Yuji Masubuchi, Mikio Higuchi, Shinichi Kikkawa, Kiyoharu Tadanaga
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 55 28 7963 - 7967 2016年07月 [査読有り][通常論文]
     
    The catalytic activity of manganese oxynitrides in the oxygen reduction reaction (ORR) was investigated in alkaline solutions to clarify the effect of the incorporated nitrogen atoms on the ORR activity. These oxynitrides, with rock-saltlike structures with different nitrogen contents, were synthesized by reacting MnO, Mn2O3, or MnO2 with molten NaNH2 at 240-280 degrees C. The anion contents and the Mn valence states were determined by combustion analysis, powder X-ray diffraction, and X-ray absorption near-edge structure analysis. An increase in the nitrogen content of rock-salt-based manganese oxynitrides increases the valence of the manganese ions and reinforces the catalytic activity for the ORR in 1m KOH solution. Nearly single-electron occupancy of the antibonding e(g) states and highly covalent Mn-N bonding thus enhance the ORR activity of nitrogen-rich manganese oxynitrides.
  • N. C. Rosero-Navarro, T. Yamashita, A. Miura, M. Higuchi, K. Tadanaga
    Solid State Ionics 285 6 - 12 2016年02月 [査読有り][通常論文]
     
    Li7La3(Zr-2 (-) Nb-x(x))O-12 (LLZNbO, x = 0-1.5) was prepared using sol-gel process at low temperatures. Additives (LiBO2 and Li3BO3) were used to improve the sintering of the ceramic electrolyte at low temperatures. XRD patterns of the calcined powder displayed the formation of cubic garnet phase between 600 and 700 degrees C in composition with higher Nb content (LLZNbO, x >= 0.5). The density of composites with additives sintered at 900 degrees C achieves 90%. In composites sintered with LiBO2, the presence of La2Zr2O7 was detected, whereas single cubic phase was obtained for the composites sintered with Li3BO3. The ion conductivity attained was 7 x 10(-5) S/cm at 30 degrees C using 6.5 wt% Li3BO3 (900 degrees C), representing enhancement by more than two orders of magnitude compared to the material without additives. Improvements of Li ion conductivity can be interpreted by the enhanced relative density as the result of the rearrangement of particles produced by adequate concentration of the additive. (C) 2015 Elsevier B.V. All rights reserved.
  • J. Mosa, N. C. Rosero-Navarro, M. Aparicio
    RSC ADVANCES 6 46 39577 - 39586 2016年 [査読有り][通常論文]
     
    The anticorrosive properties of different coatings on mild steel are insufficient and chromate corrosion protection is being eliminated owing to its toxicity. This paper shows an anti-corrosion bi-layer environmentally-friendly sol-gel coating doped with cerium (26 mm thick) on mild steel, combining a barrier effect with self-healing. Both layers have a siloxane-methacrylate composition based on the combination of a silicon alkoxide, a monomer and an organically modified silicon alkoxide as a crosslinker. Well-adhered coatings, with excellent barrier properties and current densities as low as 10(-12) A cm(-2) and impedances of 10(10) ohm cm(2), are demonstrated. Electrochemical measurements (EIS and polarization tests), SEM-EDX and micro-Raman analysis indicate depletion of Ce around defects and higher concentrations in the defect, supporting the activation of a self-healing process.
  • N. C. Rosero-Navarro, A. Miura, M. Higuchi, K. Tadanaga
    Journal of Electronic Materials 1 - 5 2016年 [査読有り][通常論文]
  • Paula Barbosa, Nataly C. Rosero-Navarro, Fa-Nian Shi, Filipe M. L. Figueiredo
    ELECTROCHIMICA ACTA 153 19 - 27 2015年01月 [査読有り][通常論文]
     
    The synthesis and characterization of nanocrystals of the zeolitic imidazolate framework-8 (ZIF8) from zinc nitrate and 2-methylimidazole (Hmim) by a colloidal chemistry route is described in the search for novel protonic conductors. The ZIF8 powders have the sodalite cubic structure with a unit cell parameter slightly in excess of 1.7 nm, a crystallite size between 30 and 50 nm, and specific surface area between 800 and 2251 m(2)g(-1), associated to high levels of microporosity and some contribution of mesopores. The impedance spectra of ZIF8 powder compacts collected under 98% relative humidity (RH) depict at least 3 contributions, which could be ascribed to the bulk resistance at high frequency, and to external interfacial phenomena at intermediate and low frequencies. The conductivity data extracted from these data display strong humidity dependence, increasing by more than 4 orders of magnitude between 20 and 98% RH at 94 degrees C, ascribed to proton transport along adsorbed water molecules. This is also supported by the enhancement of 1 order of magnitude of the conductivity of samples with highest surface area, attaining a maximum of 4.6 x 10(-4) Scm(-1) at 94 degrees C and 98% RH. The value is low, but in agreement with the reported low water uptake capacity of these materials. Surprisingly, the activation energy for conduction is as high as 110 kJmol(-1), which may denote a particular influence of the structure on proton diffusion. While the transport properties are still short for any technological application, these first results demonstrate the potential of the ZIF8 structure to combine exceptional thermal and hydrolytic stability with the potential to easily introduce high levels of proton transport by suitable functionalization. (C) 2014 Elsevier Ltd. All rights reserved.
  • N. C. Rosero-Navarro, E. M. Domingues, N. Sousa, P. Ferreira, F. M.L. Figueiredo
    Solid State Ionics 262 324 - 327 2014年09月 [査読有り][通常論文]
     
    The processing and characterization of composite membranes casted from commercial Nafion (R) suspension with incorporation of benzene-bridged periodic mesoporous organo-silicas functionalised with sulfonic acid groups (S-Ph-PMO) are presented in the search for improved protonic conductivity under low humidity conditions. It is shown that the incorporation of 10 wt%S-Ph-PMO fillers into Nafion (R) improves the proton conductivity by approximately 70%, with the composite membranes reaching 0.19 S . cm(-1) in 98% relative humidity (RH), or 0.05 S . cm(-1) in 60% RH, at 94 degrees C. The filler effect on the conductivity increases at low RH, representing an enhancement of similar to 250% and similar to 425% with respect to the conductivity of Nafion (R) at 40% RH and 20% RH, respectively. The conductivity improvement is also higher at low temperature due to the higher activation energy of Nafion (R). Such effects are interpreted by the high proton mobility in the stable mesoporous channels of the fillers. (C) 2013 Elsevier B.V. All rights reserved.
  • Tiago D. O. Gadim, Andrea G. P. R. Figueiredo, Nataly C. Rosero-Navarro, Carla Vilela, Jose A. F. Gamelas, Ana Barros-Timmons, Carlos Pascoal Neto, Armando J. D. Silvestre, Carmen S. R. Freire, Filipe M. L. Figueiredo
    ACS Applied Materials & Interfaces 6 10 7864 - 7875 2014年05月 [査読有り][通常論文]
     
    The present study reports the development of a new generation of bio-based nanocomposite proton exchange membranes based on bacterial cellulose (BC) and poly(4-styrene sulfonic acid) (PSSA), produced by in situ free radical polymerization of sodium 4-styrenesulfonate using poly(ethylene glycol) diacrylate (PEGDA) as cross-linker, followed by conversion of the ensuing polymer into the acidic form. The BC nanofibrilar network endows the composite membranes with excellent mechanical properties at least up to 140 degrees C, a temperature where either pure PSSA or Nafion are soft, as shown by dynamic mechanical analysis. The large concentration of sulfonic acid groups in PSSA is responsible for the high ionic exchange capacity of the composite membranes, reaching 2.25 mmol g(-1) for a composite with 83 wt % PSSA/PEGDA. The through-plane protonic conductivity of the best membrane is in excess of 0.1 S cm(-1) at 94 degrees C and 98% relative humidity (RH), decreasing to 0.042 S cm(-1) at 60% RH. These values are comparable or even higher than those of ionomers such as Nafion or polyelectrolytes such as PSSA. This combination of electric and viscoelastic properties with low cost underlines the potential of these nanocomposites as a bio-based alternative to other polymer membranes for application in fuel cells, redox flow batteries, or other devices requiring functional proton conducting elements, such as sensors and actuators.
  • Nataly C. Rosero-Navarro, Eddy M. Domingues, Nuno Sousa, Paula Ferreira, Filipe M. Figueiredo
    International Journal of Hydrogen Energy 39 10 5338 - 5349 2014年03月 [査読有り][通常論文]
     
    Benzene-bridged periodic mesoporous organosilicas functionalised with sulfonic acid (SPh-PMO) are explored as fillers to improve the protonic conductivity and the viscoelastic properties of Nafion (R). Homogeneous membranes with 5, 10 and 20 wt.% submicrometric SPh-PMO particles (roughly corresponding to 11, 20 and 36 vol.%) were obtained by control of the casting suspensions. The three composite membranes have acid loads and water uptake values similar to Nafion (R). The storage modulus of the 20 wt.% S-Ph-PMO composite (0.2 GPa at 100 degrees C and 0.05 GPa at 140 degrees C) is 2.5-15 times higher than for pure Nafion (R) (respectively 0.08 and 0.005 GPa), denoting a positive effect of the fillers on the mechanical resistance of the membranes, also observed for lower filler fractions. The protonic conductivity of the composite membranes at 20% relative humidity (RH) and 40 degrees C is up to 1.5 orders of magnitude higher than for Nafion (R). The magnitude of the effect decreases with increasing humidity, with the best composite attaining 0.03 S cm(-1) at 120 degrees C/40% RH, 3 times more than Nafion (R). All membranes have similar behaviour at 98% RH, showing a maximum of 0.2 S cm(-1) at 94 degrees C, with the composites still showing slightly better performance. The results are discussed in terms of the effect of the fillers on reducing the internal swelling pressure and the activation energy for proton migration. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
  • Proton conductivity of composite proton exchange membranes based on Nafion®/meso-structured organosilicas
    E. M. Domingues, N.C. Rosero-Navarro, N. Sousa, P. Ferreira, F. M. Figueiredo
    Proceeding of IV Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries 1 - 4 2013年 [査読有り][通常論文]
  • L. Paussa, N. C. Rosero Navarro, D. Bravin, F. Andreatta, A. Lanzutti, M. Aparicio, A. Duran, L. Fedrizzi
    PROGRESS IN ORGANIC COATINGS 74 2 311 - 319 2012年06月 [査読有り][通常論文]
     
    Sol-gel coatings represent an alternative corrosion protection method to the chromate based systems which must be replaced. Recently, it was shown that ZrO2 based sot-gel coatings deposited on AA6060 can provide a good corrosion protection to AA6060. However, ZrO2 based sot-gel systems are not able to provide the self-healing effect which is instead the peculiar property of chromate conversion coatings. The structure of the ZrO2 based sot-gel systems does not contain species able to restore the barrier properties when defects or damages impair the coating protection. In this work, ZrO2 based sot-gel coatings containing cerium nitrate were deposited on AA6060 aluminum alloy in order to evaluate the corrosion inhibition provided by the incorporated cerium ions. The cerium nitrate was added to the starting sot based on zirconium alkoxide precursors. Three types of samples were produced: a non inhibited type consisting of 3 layers of ZrO2, an inhibited system consisting of two layers of ZrO2 with an intermediate layer doped with cerium nitrate and an inhibited system consisting of two layers containing cerium nitrate with a top layer of ZrO2. (C) 2011 Elsevier B.V. All rights reserved.
  • L. Paussa, F. Andreatta, N. C. Rosero Navarro, A. Duran, L. Fedrizzi
    ELECTROCHIMICA ACTA 70 25 - 33 2012年05月 [査読有り][通常論文]
     
    This work evaluates the effect of cerium nitrate as corrosion inhibitor for AA2024-T3 in the view of its introduction in sol-gel coatings able to provide self-healing ability. Since it is well established that deposition of Ce species is activated by the local pH increase, the objective of this paper is to investigate the behavior of AA2024-T3 (open circuit potential and polarization curves) in the presence of Ce species in aggressive solutions by means of a local technique, the electrochemical micro-cell. This technique enables the investigation of small areas with resolution in the micrometer range by the use of glass capillaries to define the working electrode area. The micro-cell results clearly displayed that the entire AA2024-T3 area exposed to the cerium-containing electrolyte was involved in the cerium precipitation mechanism. The heterogeneous electrochemical behavior of the microstructure is minimized by the formation of a cerium-containing layer able to protect the metal substrate. (C) 2012 Elsevier Ltd. All rights reserved.
  • M. Canillas, A. Rajnicek, N.C. Rosero-Navarro, E. Chinarro, B. Moreno
    Bioceramis 23rd Symposium and Annual Meeting of International Society for Ceramics in Medicine 493-494 896 - 901 2012年 [査読有り][通常論文]
  • N. C. Rosero-Navarro, M. Curioni, Y. Castro, M. Aparicio, G. E. Thompson, A. Duran
    SURFACE & COATINGS TECHNOLOGY 206 2-3 257 - 264 2011年10月 [査読有り][通常論文]
     
    This work reports the preparation of glass-like, environmentally-friendly, cerium-based coatings for active corrosion protection of aluminium and magnesium alloys. It describes the production of cerium sol-gel sols from cerium nitrate and their deposition by immersion and automatic spray onto aluminium and magnesium alloys to produce uniform coatings with amorphous (glass-like) structures (CexOy). The coatings have been characterised by profilometry, scanning electron microscopy (SEM), spectral ellipsometry and UV-visible, in order to analyse the structure and density of the glass-like cerium coatings as well as their redox ratio Ce4+/Ce3+ as a function of pH and sintering temperature. Finally, electrochemical measurements (EIS) and standard corrosion tests (neutral salt spray, filiform corrosion, immersion-emersion test and adhesion on embossing and T-bend test) have been performed to study the corrosion behaviour of the cerium glass-like coatings on aluminium and magnesium alloys. EIS measurements confirm the healing or blocking of the defects by the corrosion inhibiting species. Excellent corrosion protection is provided by cerium glass-like coatings, satisfying the most demanding industrial requirements. (C) 2011 Elsevier B.V. All rights reserved.
  • F. Andreatta, L. Paussa, A. Lanzutti, N. C. Rosero Navarro, M. Aparicio, Y. Castro, A. Duran, D. Ondratschek, L. Fedrizzi
    PROGRESS IN ORGANIC COATINGS 72 1-2 3 - 14 2011年09月 [査読有り][通常論文]
     
    Development of Cr-free coatings is an important issue for replacement of chromate conversion coatings in aerospace and automotive industry. This aspect was targeted in the framework of MULTIPROTECT IP project funded by the European Community. This paper is an overview of research activities carried out by our groups in the framework of the MULTIPROTECT IP project.Our research approach in the project considered the development of thin ZrO2 coatings (100-200 nm) by means of sol-gel technology for AA2024 aluminium alloy. ZrO2 films were deposited employing solutions of Zr precursors. Coating application was carried out by dipping and spraying technology at a laboratory scale. In addition, substrates pre-treated with ZrO2 films were painted with an organic primer and top coat in order to evaluate paint adhesion and electrochemical behaviour of painted systems. Corrosion inhibitors were introduced in the ZrO2 coatings in order to improve the corrosion behaviour of the sol-gel films. In parallel, hybrid organic-inorganic methacrylate silane-based films containing SiO2 nano-particles doped with cerium nitrate were developed in the framework of the project. At a later stage of the project, coating deposition was carried out with a robot-controlled air pressure gun in spraying cabins in order to evaluate industrial production of the ZrO2 films and hybrid organic-inorganic films. The results obtained in the development phase clearly indicate that it is possible to deposit ZrO2 coatings and hybrid organic-inorganic films on the substrate by dipping technique. These thin pre-treatments provide good barrier properties to the substrate and promote adhesion of an organic primer and top-coat. Cerium nitrate introduced in hybrid organic-inorganic films evidences an inhibition effect on corrosion processes, which can be attributed to cerium compounds. The up-scaling phase proves that it is possible to produce water-based ZrO2 pre-treatments and hybrid organic-inorganic films by spraying technology using industrial equipment. (C) 2011 Elsevier B.V. All rights reserved.
  • Carlos Trenado, Matthias Wittmar, Michael Veith, Nataly C. Rosero-Navarro, Mario Aparicio, Alicia Duran, Yolanda Castro, Daniel J. Strauss
    MODELLING AND SIMULATION IN MATERIALS SCIENCE AND ENGINEERING 19 2 025009  2011年03月 [査読有り][通常論文]
     
    A novel hybrid sol-gel coating has recently been introduced as an alternative to high toxic chromate-based corrosion protection systems. In this paper, we propose a multiscale computational model to estimate the amount and time scale of inhibitor release of the active corrosion protection coating. Moreover, we study the release rate under the influence of parameters such as porosity and viscosity, which have recently been implicated in the stability of the coating. Numerical simulations obtained with the model predicted experimental release tests and recent findings on the compromise between inhibitor concentration and the stability of the coating.
  • L. Paussa, N.C. Rosero-Navarro, F.Andreatta, D. Bravin, A. Durán, L. Fedrizzi
    18th International Corrosion Congress 2011 2 846 - 853 2011年 [査読有り][通常論文]
  • N. C. Rosero-Navarro, L. Paussa, F. Andreatta, Y. Castro, A. Duran, M. Aparicio, L. Fedrizzi
    PROGRESS IN ORGANIC COATINGS 69 2 167 - 174 2010年10月 [査読有り][通常論文]
     
    The coating system usually employed for corrosion protection of metal substrates consists of different layers which can be constituted of a chemical conversion coating applied on the metal surface followed by a number of organic layers. Hybrid films prepared by the sol-gel method provide a good approach as protective layers on metallic surfaces, although it is necessary to combine the barrier functionality with an active protection mechanism to avoid corrosion when the coating is damaged. Previous works have shown that it is very difficult to reach this result in a mono-layer sol-gel because the amount of inhibitors incorporated tends to increase significantly the porosity of the coating and reduces drastically the barrier properties. This work presents the characterization of a multi-layer sol-gel hybrid inorganic-organic coating system with a structure composed of an intermediate cerium inhibited layer deposited between two un-doped layers on AA2024 alloy. The comparison between the inhibited system and a bi-layer non-inhibited one has allowed to assess the migration of the cerium ions into the hybrid coating towards the substrate corresponding to the improvement of the corrosion properties. The combination of the physical barrier and the active protection enables to obtain an effective protective system. (C) 2010 Elsevier B.V. All rights reserved.
  • N. C. Rosero-Navarro, M. Curioni, R. Bingham, A. Duran, M. Aparicio, R. A. Cottis, G. E. Thompson
    CORROSION SCIENCE 52 10 3356 - 3366 2010年10月 [査読有り][通常論文]
     
    In this work, a split-cell technique and image-assisted electrochemical noise analysis, which provide minimal perturbation of the freely corroding system and good time resolution, are proposed as a tool for simultaneous investigation of the corrosion inhibition mechanism and assessment of performance. The results obtained are compared with results from traditional electrochemical impedance spectroscopy, disclosing the advantages of these techniques in the evaluation of inhibitor performance. Specific attention is also given to the investigation of corrosion inhibition by cerium nitrate. (C) 2010 Elsevier Ltd. All rights reserved.
  • Nataly Carolina Rosero-Navarro, Pawel Figiel, Roman Jedrzejewski, Anna Biedunkiewicz, Yolanda Castro, Mario Aparicio, Sergio Antonio Pellice, Alicia Duran
    JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY 54 3 301 - 311 2010年06月 [査読有り][通常論文]
     
    The aim of this work was to study the effect of the incorporation of cerium nitrate in a silica-methacrylate sol-gel hybrid matrix reinforced with silica nanoparticles. Sols, coatings and powders have been studied, focusing specially in the determination of the redox ratio Ce3+/Ce4+ and films structure. Sols have been characterised using viscosity measurements and FT-IR spectroscopy, and powders and coatings obtained with different Ce contents through UV-Vis and FT-IR spectroscopy, TGA, TEM, AFM and FE-SEM. The goal was to reach the best compromise between maximum cerium concentration and coating stability to better understand the mechanisms acting in active anti-corrosive processes.
  • L. Paussa, N. C. Rosero-Navarro, F. Andreatta, Y. Castro, A. Duran, M. Aparicio, L. Fedrizzi
    SURFACE AND INTERFACE ANALYSIS 42 4 299 - 305 2010年04月 [査読有り][通常論文]
     
    Aluminium alloys such as AA2024 are susceptible to severe corrosion attack in aggressive solutions (e.g. chlorides). Conversion coatings, like chromate, or rare earth conversion coatings are usually applied in order to improve corrosion behaviour of aluminium alloys. Methacrylate-based hybrid films deposited with sol-gel technique might be an alternative to conversion coatings. Barrier properties, paint adhesion and possibly self-healing ability are important aspects for replacement of chromate-based pre-treatments. This work evaluates the behaviour of cerium as corrosion inhibitor in methacrylate silane-based hybrid films containing SiO(2) nano-particles on AA2024. Hybrid films were deposited on aluminium alloy AA2024 by means of dip-coating technique. Two different types of coating were applied: a non-inhibited film consisting of two layers (non-inhibited system) and a similar film doped with cerium nitrate in an intermediate layer (inhibited system). The film thickness was 5 mu m for the non-inhibited system and 8 gm for the inhibited system. Film morphology and composition were investigated by means of GDOES (glow discharge optical emission spectroscopy). Moreover, GDOES qualitative composition profiles were recorded in order to investigate Ce content in the hybrid films as a function of immersion time in 0.05 NI NaCl solution. The electrochemical behaviour of the hybrid films was studied in the same electrolyte by means of EIS technique (electrochemical impedance spectroscopy). Electrochemical measurements provide evidence that the inhibited system containing cerium displays recovery of electrochemical properties. This behaviour is not observed for the non-inhibited coating. GDOES measurements provide evidence that the behaviour of inhibited system can be related to migration of Ce species to the substrate/coating interface. Copyright (C) 2010 John Wiley & Sons, Ltd.
  • N. C. Rosero-Navarro, S. A. Pellice, A. Duran, S. Cere, M. Aparicio
    JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY 52 1 31 - 40 2009年10月 [査読有り][通常論文]
     
    The aim of this work is the synthesis and characterization of hybrid coatings doped with cerium salts for corrosion protection of AA2024. The control of the inorganic and organic polymerization process allows the preparation of coatings with an open structure and a hydrophilic character. These facts facilitate the incorporation and mobility of cerium ions through the structure, enhancing its ability to promote a self-healing mechanism. The thermal treatment of the coatings has been limited to 120 A degrees C to preserve the mechanical properties of the alloy. The electrochemical behaviour of the coatings has been evaluated in 0.3 wt% NaCl solution by means of EIS technique. Electrochemical measurements evidence good barrier properties at initial immersion time, and signals of corrosion inhibition from cerium ions at long immersion times could be assigned to the increasing of the impedance modulus at low frequencies and the presence of cerium oxide/hydroxide precipitates.
  • M. Zaharescu, L. Predoana, A. Barau, D. Raps, F. Gammel, N. C. Rosero-Navarro, Y. Castro, A. Duran, M. Aparicio
    CORROSION SCIENCE 51 9 1998 - 2005 2009年09月 [査読有り][通常論文]
     
    Hybrid sol-gel coatings provide an approach as protective layers on metals. In this work, corrosion protection of aluminium and magnesium alloys by SiO2-methacrylate coatings doped with TiO2-CeO2 nanoparticles was studied. The films show an improvement of the barrier properties at initial immersion. The reactivity of both alloys produces a deterioration of the protection with longer immersion, although TiO2CeO2 nanoparticles let to observe signals of self-healing effect. Aluminium oxide/sol-gel interface was found to be stable. In combination with excellent paint adhesion on sol-gel films, these coatings can be a promising alternative pre-treatment for high strength aluminium alloys prior to painting. (C) 2009 Elsevier Ltd. All rights reserved.
  • N. C. Rosero-Navarro, S. A. Pellice, Y. Castro, M. Aparicio, A. Duran
    SURFACE & COATINGS TECHNOLOGY 203 13 1897 - 1903 2009年03月 [査読有り][通常論文]
     
    In this work we present the development of a nanocomposite material composed by silica nanoparticles in a hybrid organic-inorganic sol-gel matrix for corrosion protection of aluminium alloys. The sol-gel matrix was produced from an inorganic precursor, tetraethoxysilane (TEOS), a hybrid precursor organically functionalized with C=C groups, 3-metacryloxypropyltrimethoxysilane (MPS), and an organic bi-functional monomer, ethyleneglycol-dimethacrylate (EGDMA) used to increase the cross-linking network. Silica nanoparticles, on the other side, increase the density and provide a major mechanical performance through the reinforcement of the coating. The evolution of the sol, mainly the chemical structure, during the processes of hydrolytic condensation and organic polymerisation was studied as a function of the sol concentration through Fourier transformed infrared spectroscopy (FTIR), rheometry, laser diffraction analysis and contact angle. Mono and multilayer coatings were deposited by dipping onto AA 2024 substrates and characterised by profilometry. The corrosion behaviour was followed through potentiodynamic tests and Electrochemical Impedance Spectroscopy (EIS). (C) 2009 Elsevier B.V. All rights reserved.
  • Josefina Ballarre, Damian A. Lopez, Nataly C. Rosero, Alicia Duran, Mario Aparicio, Silvia M. Cere
    SURFACE & COATINGS TECHNOLOGY 203 1-2 80 - 86 2008年10月 [査読有り][通常論文]
     
    Metallic materials are the most used materials as orthopaedic or dental implants because of their excellent mechanical properties. However they are not able to create a natural bonding with the mineralized bone and occasionally suffer localized corrosion. This work describes the electrochemical behaviour of a system of coatings with the addition of bioactive particles of the system SiO2-CaO-P2O5, that enhance the abilities of the implant to make an union with the existing bone and to resist the extreme environment that are exposed to. The coatings were obtain from two kind of sols that were made by sol-gel process: one, using tetraethoxysilane (TEOS) and methyl triethoxysilane (MTES) as precursors, and the other using hydroxyethyl methacylate (HEMA), tetraethoxysilane (TEOS) and 3-methacryloxypropyl-trimethoxysilane (gamma MPS) [TMH] as precursor. Coatings were made in two layers. The inner layer was prepared either using TEOS and MTES (that had already shown good anticorrosion properties), or TMH. The top layer was made with TMH with the addition of 10% in weight of small (diameter less than 20 mu m) or big (more than 20 mu m) bioactive particles. The samples were tested in vitro by polarization curves and electrochemical impedance spectroscopy (EIS) assays. The samples with the two kind of coatings seem to have a protective behaviour after 30 days of immersion due to the compact TEOS-MTES inner layer. The big particles placed in the outer layer showed a dissolution rate similar to the rate of deposition of the amorphous hydroxyapatite (aHAp) at the surface, blocking the entrance of the electrolyte, avoiding it to reach the substrate. The TMH coatings with small particles present a similar behaviour to the naked material, allowing the electrolyte to reach the metal. The dual coating with this kind of particles has similar characteristics, with a "sponge-like" behaviour, and the inner coating probably develops flaws due to the fast dissolution of the small particles placed in the upper layer. (C) 2008 Elsevier B.V. All rights reserved.
  • N. C. Rosero-Navarro, S. A. Pellice, A. Duran, M. Aparicio
    CORROSION SCIENCE 50 5 1283 - 1291 2008年05月 [査読有り][通常論文]
     
    A hybrid organic-inorganic self-healing coating for anticorrosive protection of AA2024 was developed through the sol-gel method. Combination of permeability, provided by a methacrylate-silica hybrid matrix, with hardness and density of silica nanoparticles, allowed obtaining a coating material where the diffusion of Ce ions occurred at the same time that an anticorrosive physical barrier was developed. Electrochemical impedance spectra (EIS) on coated samples showed an increase of the impedance modulus at 0.01 Hz as a function of immersion time in a 3.5 wt% NaCl solution. Self-healing effect was verified by impedance fitting through the evolution of resistive and capacitive parameters of the equivalent circuits. (c) 2008 Elsevier Ltd. All rights reserved.
  • Damidn A. Lopez, Nataly C. Rosero-Navarro, Josefina Ballarre, Alicia Duran, Mario Aparicio, Silvia Cere
    SURFACE & COATINGS TECHNOLOGY 202 10 2194 - 2201 2008年02月 [査読有り][通常論文]
     
    AISI 316L stainless steel is a biocompatible alloy used in prosthetic devices for many years. However this alloy tends to suffer localized corrosion and needs external fixation to hard tissues. This work describes the development of a coating system of two layers with complementary properties. The inner layer is prepared using TEOS and MTES that has already shown good anticorrosion properties. The top layer is a new hybrid organic-inorganic coating prepared with TEOS, 3-methacryloxypropyl trimethoxysilane (MPS), and 2-hydroxyethyl methacrylate (HEMA). The properties of this sol let to produce a thick and porous coating formed by two interpenetrating (organic and inorganic) networks. This coating could be an excellent container for the later aggregate of bioactive particles as the following step in a future work based on its high thickness, plasticity and open structure to allow the electrolyte access to induce the formation of hydroxyapatite. The coating is electrochemically characterised in simulated body fluid at 37C after 1, 10 and 30 days of immersion by means of assays as electrochemical impedance spectroscopy (EIS) and polarization curves. The dual coating seems to join the best properties of the individual ones in time: their thickness restrict the passage of potentially toxic ions to the body fluid, the breakdown potential (Eb) remains high and far from the corrosion potential (Ecorr) and the film presents the open structure of the outer layer that allows the entrance of the electrolyte to react with the particles when added to the sol meanwhile the inner layer maintain its corrosion protective features. (c) 2007 Elsevier B.V. All rights reserved.

MISC

書籍等出版物

  • Kiyoharu Tadanaga, Nataly Carolina Rosero-Navarro, Akira Miura 
    2021年03月 85-92
  • Sintering additives for Garnet Type Electrolytes
    N. C. Rosero-Navarro, K. Tadanaga (担当:分担執筆範囲:Solid Electrolytes for Advanced Applications: Garnets and Competitors. 1st edition, . DOI 10.1007/978-3-030-31581-8_5)
    Springer 2020年
  • Sol-gel processing of solid electrolytes for Li-ion batteries
    N. C. Rosero-Navarro, K. Tadanaga (担当:分担執筆範囲:Handbook of Sol-Gel Science and Technology 2nd, DOI:10.1007/978-3-319-19454-7_142-1))
    Springer 2017年 doi:10.1007/978-3-319-19454-7_142-1)
  • Chapter 11: Hybrid Ce-containing silica-methacrylate sol–gel coatings for corrosion protection of aluminium alloys
    M. Aparicio, N. C. Rosero-Navarro, Y. Castro, A. Durán, S. A. Pellice (担当:分担執筆範囲:In European Federation of Corrosion Publications Number 58: Self-healing properties of new surface treatments)
    Maney Publishing 2011年 202-2019

所属学協会

  • The Electrochemical Society of Japan   The Ceramic Society of Japan   International Society of Electrochemistry   International Sol Gel Society   


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