The 3% International Conference on Advanced Materials and } Hanoi, 2016 notechnology Controlled Synthesis and Magnetism of Hierarchical a-Fe,O3 Part Modified Polyol Methods and Heat Treatment les by Nguyen Viet Long", Yong Yang', Cao Minh Thi", Masayuki Nogami! Ceramies and Biomaterials Group, Ton Due Thang University, Ho Chi Mini City, Vietnam ‘Faculty of Applied Sciences, Ton Duc Thang University Ho Chi Minh City, Viewam “Toyota Physical and Chemical Rescarch Institute, Nagakute, Aichi, “tio Chi Minh City Universit of Technology, 475A Dien Bien Phu Street, Binh Than Distit, Ho Chi Mi * Corresponding author: ngwvenvictlong@tét.eduve & nguvenvict longi@vahoa.cam Abstract: We have presented the controlled synthesis of novel With the a-Fe,O, structure of great interest in the certain microscaled ranges by modified polyol methods borohydride as powerful and efficient reducing agent according to the critical heat treatment processes at high temperature for the interesting formation of hierarchical a-Fe,O, hematite with a new micro/nanoscale structure. The formation and weak ferrimagnetism of grain and grain boundary of hierarchical microsealed -Fe,0, structures were investigated by X-ray diffraction method with whole pattern fitting and Rietveld refinement, X-ray photoelectron spectroscopy, and scanning electron microscopy, and vibrating sample magnetometer. The as-prepared tmicro/nanoscale a-Fe,0; and their new three dimensional (3D) models have promising practical applications for energy storage and conversion in batteries, capacitors, and fuel cells, and spintronic devices and technologies. Keywords: «Fes 1. INTRODUCTION So far, Iron (IID) oxide or fertic oxides or FesOs oxides have shown very stable oxidation states because of oxygen coordination in their crystal structure with ferromagnetic properties. Fe,0s powders were prepared with the various a, 7, B, and e forms and structures [1-3]. Among them, « Fe0s proved shows the very stable and durable crystal structures in octahedral coordination geometry in air and various gas environments, Recently, @-Fex0s oxide powders with micro/nanoscale structures and materials have shown very promising potential applications in a wide range of gas sensor, energy, environment, biology and medicine (nanomedicine), spintronics, solar cell, fuel cell, battery, and capacitor in energy storage and conversion processes because of inexpensive cost, very low toxicity, very good optical, electrical, and magnetic properties [1-7] Dramatically, a- Fe:0; micro/nanoscale materials were employed in negative electrode for high performance supercapacitors. We could synthesize @-Fe;0; micro/nanoscale materials by various methods and processes like hydrothermal and solvothermal method, electrodeposition method, green synthesis methods, Sol-gel__ chemistry, precipitation method etc. The synthesis processes, growth, and formation of uniform large a-Fe.0s particles by modified polyol method with the use of KOH, NH,OH, Nal, NaCl, NaBH, and NaOH were possibly successfully presented in. heat treatment at high temperature [8-15]. Through low ematite, Grain, Grain boundary, Hierarchical a-e,0, particles temperature sol-gel synthesis, the formation of Fe oxide crystal structure and change between F205, y-Fex0s and Fes, were identified [16] However, at present, the research results of uniform large a-FeO3 particles with grain and grain boundary textures have been relatively rare, which needs to use special annealing processes in critical conditions of time and temperature. To obtain the new magnetic particles with the pure crystal structures, typically Fe, Fe0s in its stable and durable a, y, and fi} crystal structures, or «-Fe,0s, the researchers needed to use the critical synthetic processes and heat treatment. In general, the main reasons are that the final Fe oxide products were formed in the combination of FeO, 20s, a-FexOs, and Fe,Oy. The crystal phase of the pure Fe particles can be changed into that of Fe,0, particles via heat treatment. ‘The researchers show that the preparation procedure of the pure phase has proven very challenging due to mixture with minor crystal phases in main phase. Therefore, heat ‘treatment processes to a-Fe:0s particles or hematite powders have been to be focused with the best efforts of scientists and researchers. To gain the new properties for their practical application, Fe oxide micro/nanoscale powders were heated or annealed in air or in various gases like Nz and Hp ete to make new gas element (or H, N, C, or a mixture of gases etc..) doped Fe oxide structures, and possibly create the new properties of both high strength and durability.The 3% International Conference on Advanced Materials and } Hanoi, 2016 notechnology In this main contribution, we have successfully developed the new chemical polyol processes 10 synthesize Fe-based particles associated with heat treatment. In addition, the roles of heat treatment to obtain the prepared hierarchical micro/nanoscale a- Fe,Os particle powder products lead to particle deformation, leading to the various levels of the deformation of size, shape, morphology, surface, internal structure, composition, other crystal parameters during sintering and final densification, leading to structure deformation on both the surface and inside the particles. The durability, stability, and strength of the particles after heat treatment at high temperature significantly enhanced are all the best chemical and physical properties of the particles. with both, ‘micro/nanostructures. These important improvement and modification processes are the keys for discovering the fundamental new applied properties of hierarchical a-FexOs particles, 1, EXPERIMENTAL A. Synthesis of hierarchical a-Fex0s microparticles ‘Chemical, Modified Modified Fe precursors, Polyol Polyol wie | L_ methods [> |_methoas Wet Fe-based Heat Hierarchical particles =>) trearments [=>] «Fes0s particles Figure 1 Synthesis of hierarchical a-PesOx microparticles, Figure 1 shows the controlled synthesis of a- Fe,0s_ particles. The starting precursors were prepared as described in previous detailed works for a-Fe,0s oxide particles about 20-30 min, and with drying and heat treatment. Briefly, a lot of attention and time were paid to develop our increasingly stringent preparation processes. In a typical process, 10mL of EG, 3mL of 0.0625M FeCl (FeCh.GHO precursor), 10mL of 0.375M PVP, and 0.048 NaBH, were used for synthesis. The stock solutions of Fe precursors were pumped into the center of reaction flask (250mL) under stirring for the precisely controlled synthesis. The reaction periods for synthesis of PVP-Fe particles via the fast reduction of precursors by NaBH were done for 45 min. Then, the PVP-particles were achieved in the resulting black solutions. They were kept at room temperature for some days to obtain the black products at the bottom. The clean black products were obtained by removing PVP on the surfaces of as-prepared paiticles according to centrifugation processes, washing, cleaning procedures, and heat treatment processes. They were maintained in the containers in the forms of powders. Then, the dried particle powders were re- dispersed into ethanol and dried at 60°C, respectively. To obtain black-brown oxide products of a-Fez0s particles, these black powders were isothermally heated at 900°C for 1h with ceramic containers in air, and other gas elements. B. Chacracterization We prepared a series of the various a-Fe0s particle powder samples for X-ray diffraction (XRD), scanning electron microscopy (SEM) investigation and analysis. The most typical characterizations of the particles were investigated by XRD, SEM, and VSM methods. The X-ray diffraction pattems of a-Fe:0; particles were recorded in a 20 range of 5-95° by X-ray diffractometer (Rigaku-Dimax___2550V, 40kV/200mA, CuKa. radiation at 1.54056A). Here, there is the general theoretical foundation for the investigation of erystals by X-rays is Brage's law. where 4 — wavelength, d - spacing of reflecting planes, 0 - angle of incidence and reflection, n - order of diffraction. For crystal structure with lattice parameter, monochromatic radiation of diffractometer, and order of reflection, we can calculate the interplanar spacing and the difiraction, angle for the set of planes. To calculate crystallite of hierarchical a-Fe,0; micro/nanoscale particles, we have additionally used Debye- Sherrer's equation. Here, structural parameters are crystallite size (D), wavelength of X-ray radiation Q). Full width at half maximum with the most intense peak in XRD patterns (B), Bragg angle (0), respectively. The features of size, shape, and morphology were investigated by field emission (FE)SEM. We have used field emission scanning electron microscope (SEM) (JEOL-JSM-6340F) operated at 5, 10, and 15 kV (5-15 kV), and probe current around 121A (I-12A). Here, VSM method was applied for determination of magnetic properties of magnetic a-Fe,0s_micro/nanoscale particles mentioned. We have utilized a vibrating sample magnetometer (VSM), Model EV11, which is used for analyzing magnetic characteristics of a- Fe,03 micro/nanoscale materials evaluated at room temperature (RT), about 293K in a wide range of applied field from -20k0e to 20kOe. Here, EVI1- VSM can reach fields up to 31kOe at a sampleThe 3% International Conference on Advanced Materials and } Hanoi, 2016 notechnology space of $ mm and 27 kOe with the temperature chamber, with Signal noise to be 0.1 emu, and 0.5 emu, respectively. Mil, RESULTS AND DISCUSSION Figure 2 shows our result of XRD pattern of the as-prepared a-Fe0s micro/nanoscale particles with particle size in a rmge of 10 um (for hematite, a-Fe;0s according to ICDD/ICPDS- PDF#33-0664 (XRD powder data). In our observation and evaluation, Figure 2 shows the most typical peaks are characterized by a set of miller indices of (012), (104), (110), (113), (024), (116), (122) or (018), (214), (300), (208), (1010), and (220), and more (hkl), respectively. The corresponding values of 20 (°) are estimated in Table 1, respectively in respective to a certain range of 20-80°, The XRD data indicated the best crystallographic a-Fe20s structure, crystallite size or grain size. The a-Fe03 oxide phase was formed with high crystallization, The standard pattern is PDF#33-0664 for a-FeO3 with the 45_ lines, CuKal, Lambda=1.5406, 2T=24.138-147.961 (’) This is hexagonal crystal system, space group R- 3C(167) with 8 lines to be strong. The strongest intensity is the (104) line, The lattice parameters are a=5.042, b=5.042, and e=13.773 A, and a=90, }=90, and 7=120" with the eleven lines confirmed. The strongest line is the (104) line that was characterized in the crystal phase of a-Fe2Os Table 1 Peaks to Index to a-Fes0y 210) hkl _27(c)__d{e)___afo)_1% O12 24111 S6ee 3.6954 313 104 33105 2.7037 2.7072 100.0 110 35575 25215 25239 745 113 40.796 22100 22118 262 024 49381 L440 Ladd] 48.3 116 53978 1.6973 1.6968 60.5, O18 57499 1.6015 1.6015 10.9 214 62.330 14885 1.4882 39.8 300 63.892 14558 14556 42.5 71.902 101071817 1313413120 13.6 75376220 75319 1.2607 1.2599 _11.6 It is noted that the phase identification was confirmed in a-Fe,0x with the lines by our observation for hematite, and 11 lines by pattern indexing with MDI Jade software (Table 1), and 28 lines by standard pattern PDF#33-0664. In the reflections from lattice constants, the values of d-I parameters were shown in Table I. In the phase identification, the strongest line was revealed to be from the reflections of (104) planes. The polyhedral a-Fe,Os microparticles were heated under high temperature at 900 °C. 2 : 2 2 2 i = ae 2 5 1 27) igure 2. XRD patterns of the as-synthesized 61.9% e-2260% Whole Figure 3. refinement of XRD of hierarchical a patter fiting and Rietveld 103 particles. Figure 3. shows the whole patter fitting and Rietveld refinement of XRD pattern of, hierarchical a-Fe;0; particles. The several R- indices were also determined at iteration times [17], ie. Round 4, R=61.64%, Here, the profile shape function for all the phases including pseudo- Voigt, Fixed-BG, 2=1.54056A (CwKal). There is the only crystal phase for a-Fe 0s, a=b=5,03503A, 3.73709A, — c/a=2.72830, «=B=90", y=120". The value c/a of the hierarchical «Fe,0s micro/nanoscale particles is smaller than that of the standard sample. Figure 4 illustrates the most typical SEM images of hierarchical a-Fe,0s (10 ym) oxide particles with grain and grain boundary forms. We have selected the most typical two particles for calculation based on scaleHanoi, 2016 bar 1 and 10 ym. It is suggested that they show the characterizations of size, shape and morphology with deformation [8-10]. We suggest that the two samples of a-Fe;03 particles proved grain and grain boundary inside various porous structures after high heat treatment at 900°C hh in air for 1 Here, the products of a-Fe;0; oxide particles were regarded as hierarchical micro/nanostructured oxide materials. Figure 3 also shows the most typical polyhedral models of hierarchical a-Fe20s particles with grain and grain boundary in our experimental results of SEM observation and investigation. Figure 4. SEM of hierarchical a-Fe203_partiles: Grain and grain boundary Figure 5 shows the new models of hierarchical a- Fe,Os particles with grain and grain boundary. There is one a-Fe20s oxide particle (models A-F) with its assumed particle size about jum (model A), and a-Fe,0s oxide particle (model F) about 10 hm, The assumed models A, B,C, D, E, and F are uniform in the sizes, the shapes, and the morphologies. The number of grains is possible to be hundreds to thousands oxide grains. eS ey UD Ae Di De igh Ete Dy Ets Figure 5 particles with grain and The color of the normal and abnormal grains and grain boundaries of the oxide particles shows the possibilities and positions of the development of grain growth in the case at high temperature and the particle are continuously provided and heated ‘The changing formation and disappearance of the specific grain at the fixed high temperatures can be simulated and modelled by phase field model [18]. Further, we present the models and the hard evidences of the formation of grain and grain boundary in the hierarchical 3D _a-Fe,0s micro/nanoscale oxide particles. This formation can be possible appearance in various materials, such as metals, alloys, oxides, and ceramics microinanoseale ‘materials with grain and grain boundary. Here, we focus on atomic arrangement in nanoscale range of hierarchical metal, alloy, ceramic and oxide particles at nanoscale and related properties to practical applications as well as the grain and grain boundary arrangement in the hierarchical metal, alloy, oxide particles at microscale and related properties with the heat treatment methods and processes for grain and grain boundary. The relationship of atomic arrangement in magnetic nanoparticles (1-100 nm) as well as grain arrangement in hierarchical 3D ‘magnetic particles more than 100 nm, i.e. less than Jum, 1-10 ym up to 1-100 jm) need to be intensively studied in the same magnetic properties. The complexity of atomic arrangement, grain, and grain boundary arrangement in nano/microscale is appealing to the researchers. The number of grain and grain boundary, fine grain and grain boundary formation on the surface and inside the large hierarchical magnetic particlesThe 3% International Conference on Advanced Materials and } needs to be understood in materials science, Though heat treatment, hierarchical 3D a-Fe,0s oxide particles by heat treatment will have some unique and technologically promising properties. Our present results of hierarchical 3D a-Fez0s with grain and boundary structures will contribute significant opportunity of improving Pr/oxide catalyst materials for FCs and batteries, and enhancing the performance of gas Similarly, AB,O,-based ferrites push forward the research to new magnet materials. Thus, the fine magnetic particle powders, and grain and grain boundary structures need to be intensively studied for understanding magnetic domains and magnetic walls. In this trend, the present studies involve in controlled synthesis and characterization of various metal and oxide particles with the micro/nanoscale structures associated with the related practical applications. Metal and magnetic Fe-based oxide particles with micro/nanoscale structures with grain and grain boundary textures have large potential applications for our health, life, engineering, academic research, science and technology, magnetic recording, speakers, electronic devices, motors, power generation, equipment, gas sensors ete, and for dealing with problems and challenges of energy crisis and pollution environment [1,2]. It is known that a- FeO; was parasite ferromagnetic material. In our investigation of magnetism of a-Fe,0s particles, the most important measurement parameters include Mx, Ms, Hc, Hs, and squareness (S-Mg/Mg) etc, which were calculated, and analyzed in magnetic hysteresis loops. Figure 6 shows hysteresis loops of a-Fe:O; taken to magnetization saturation at the specific S and S? points in the comparison of their magnetism, which are $ and $! points in M-H curves. They typically show remanent magnetization which M measured at H=0, saturation magnetization at maximum M measured in forward and reverse saturations, coercive field strength at which M/H changes sign, squareness parameter etc. The hysteresis loop of a-Fe20s particles indicated the magnetic parameters of upward part, downward part, and average value, respectively. The typical magnetic parameters of hysteresis of a-Fe,Os materials by VSM method were listed in Table 2. We have found a-Fe203 oxide particles have the low magnetization saturation (Ms) about 3 emu/g exhibiting a trend to be antiferromagnetism (or to be weak ferrimagnetism). otechnology Hanoi, 2016 Ss Ty A | as 2 — Field Figure 6, Magnetism of hierarchical «-Fe,03 particles: VSM ‘Table 2. Hysteresis parameters Hysteresis Up Down Average Jo0j He (Os) Tosold 10014 103.018 M(emuig) 2.668540 -2.696+0—2.6828+0 MatHmax — 2.6685+0 -2.6960 2.682840) (emul) ‘Mx: Remanent —-S49E-3_S49E 54s (00) 1373.85 -9998,00__11865.93 In contrast, the ferrimagnetic a-Fe,Os particles have high magnetization saturation (Ms) exhibiting a trend changing from ferrimagnetic to the super paramagnetic property in comparison with superparamagnetic alloy and oxide nanoparticles with very small sizes less than 10 and 100 nm investigated in past. The antiferromagnetism or the week ferrimagnetism of hierarchical a-Fe,O3 particles is identified. Based on our obtained results, we suggest that particle heat treatment is very important to harden the microstructure of a-Fe,0; oxide micro/nanoscale materials in final crystal growth and formation after heating at 900°C with heavy particleThe 3% International Conference on Advanced Materials and } ianotechnology Hanoi, 2016 deformation of size, shape, surface, and inner structure associated with plastic and elastic deformation at micro/nanoscale ranges. Therefore, weak ferrimagnetism of hierarchical a-Fe20s microparticles was identified in order to achieve an increase in the quality, durability and stability. Conclusion Tn this study, the hierarchical _a-Fe;0s microparticles with the specific grain and boundary textures were made by an efficient process via modified polyol method with NaBH, innovative and sophisticated heat treatment at 900°C for 1h in order fo obtain the adequate material solidification under heating. A prepared micro/nanoscale structure is kept without self-destroying as a challenge to the scientists. a-FexOs structures with high crystallization levels were confirmed by XRD method and whole pattern fitting and Rietveld refinement, The a-Fe)O; microparticles show antiferromagnetism ot very weak ferrimagnetism at room temperature. Finally, the object of this research is to study, understand, and carry out the controlled synthesis of important kinds of Fe-based le oxide particles with very small size, and hierarchical micro/nanoscale Fe-based oxide particles with large sizes, and with grain and grain boundary in the special concems from researchers in significant potential in the various aspects and related fields of conversion energy, battery, gas sensors, and magnetic applications ACKNOWLEDGMENT This research is supported and funded by Ceramics and Biomaterials Group, Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam. REFERENCES IA. 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