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Assignment of Analytical Chemistry

Review of International Journal Study of Phase Transition on Nanocrystalline (La, Sr)(Mn, Fe)O System Using High-pressure Mossbauer Spectroscopy and High-pressure X-ray Diffraction Lecturer: Sulistyo Saputro, M.Si., Ph.D

By: Riezky Dwi Anggoro K3310073 Chemistry Education


The aim of this research was to study of phase transition on nanocrystalline (La, Sr) (Mn,Fe) O system using high-pressure Mossbauer spectroscopy and high-pressure X-ray Diffraction. Pressure is an important parameter to study and understand the unknown knowledge about manganities. The properties of manganities was changed by external pressure by changing Mn-O bond length. Under pressure transition from orthorhombic to monoclinic was observed in La0.5Ca0.5MnO3 and type of antiferromagnetic state was state seen in La0.5Ca0.5MnO3 and Pr0.7Ca0.3MnO3. Some of the relevant studies were done by Ramos et al stated stability of Jahn-Teller distortion in LaMnO3 under pressure, Hwang et all stated Increase in metal insulator transition temperature TM-1 and Murata et all investigated that La2-2xSr1-2xMn2O7 have a planar ferromagnetic structure with easy axis in the ab-plane, which changes to uniaxial ferromagnetic structure whose easy axis is parallel to c-axis at a pressure between 0.5 to 1.0 GPa. The background of this research was few studies have been reported on high-pressure behavior of the manganites perovskites, but with nanocrystalline structured reported was rare. So, this research reported the pressure dependence on the magnetic and structural properties of the nanocrystalline La0.8Sr0.2Mn0.8Fe0.2O3 system using diamond anvil cell, through High Pressure Mossbour Spectroscopy and High-Pressure X-ray Diffraction. The nanocrystalline La0.8Sr0.2Mn0.8Fe0.2O3 synthesized by sol gel nitrate method was characterized for the particle size distribution by X-ray diffraction (XRD) and Atomic force Microscopy (AFM) techniques. The particle size estimated for the sample is 13 nm. Mssbauer measurements at ambient conditions were made using Co57(Rh) source at constant acceleration mode using krypton filled proportional counter as detector. For highpressure Mssbauer measurements, a Si PIN solid-state detector with a resolution of 250 eV was used. The sample was loaded along with ruby crystal in a Merrill Bassett diamond anvil cell (DAC) using tantalum gasket and methanol : ethanol (4:1) mixture as pressure transmitting medium. High-pressure X-ray diffraction (HPXRD) was carried out with a Mao-Bell type of diamond anvil cell (DAC) in angle depressive mode using the Guinier geometry. The detailed description of the high-pressure Guinier diffractometer set-up is given elsewhere. The incident Mo X-ray is obtained from a Rigaku 18 kW rotating anode X-ray generator. A 50 mm long position sensitive detector is used to detect the diffracted X-rays. The overall resolution is found to be d/d = 0.015. The finely powdered sample and ruby crystals were loaded into a stainless steel gasket hole, together with a mixture of methanol, ethanol and water (MEW) in volume ratio of 16:3:1 as the pressure transmitting medium. The sample pressure in the DAC was determined by the ruby fluorescence method. The pressure dependence of Isomer Shift (IS) and Quodrupole (QS) at room temperature is shown in Fig. 1. Two different values of Isomer shift indicate different environment of iron, low spin Fe3+ in octahedral site (site a) and Fe4+ in cubic symmetry (site b). Kopcewicz et al assumed that the low symmetry with large QS corresponds to the

position surrounded by six Mn3+ ions (site a) while the higher symmetry site with smaller QS, have at least on of the Mn in Mn4+ state (site b). a sudden increase in isomer shift (IS) of Fe4+ configuration (site b) at 0.52 GPa represents first order phase transition to high spin Fe3+ while the IS for site a remains almost constant up to 10 GPa. The ferromagnetic interactions of the electrons might decrease the s electron density at the Fe nucleus simultanesously increasing the IS. The increase in QS indicated the distortion of Fe3+ lattice. On further increasing the pressure to 3.7 GPa IS of site b drops to low spin Fe3+, to coincide with site a indicating convergence of the two different configurations of Fe into one. The prominence of electronic contribution of other atoms (La, Sr) increases the s electron density at the Fe nucleus thereby decreasing the isomer shift. Only Fe in site b responds to the variations with pressure, whereas the other site (site a) remains unchanged, indicates the directional nature of the stress generated with the application of pressure. Quadrupole splitting show a continuous increase with pressure up to 9.2 GPa, representing an anisotropic distortion of lattice. High-pressure diffraction experiments on the stoichiometric sample La0.8Sr0.2Mn0.8Fe0.2O3 were carried up to 4.3GPa. Fig. 2 compares the XRD of pattern at ambient pressure, 0,3 GPa and 0.6 GPa. At the 0.6 GPa, there are new peak where the # (112) and (123). This may be explained as reorientation of certain planes with the application of pressure. And then we could see the full width at half maxima of the peaks of XRD pattern in the Fig. 3a and Fig. 3b. From the figure either Fig. 3a or Fig. 3b, we could see the peak widths of (220) and (022) show unusual decrease at 0.6 and 0.9 respectively, while (020) and (200) show general increasing trend with pressure giving the hint reorientation of grain/grain boundaries in a articular direction in this pressure range. Gradual but small variation are observed up to 1,1 GPa. At 3.6 GPa (Fig. 4) there was a drastic change or a discontinuity in the values clearly indicating a phase transition at that point. Another interesting feature seen was the unusual expansion of (220) d-spacing at 0.6 GPa (Fig. 3a), while other planes show normal decreasing trend (Fig. 3b) confirming the effect of unixaxial stress acting in ac-plane. At the 3.6 GPa the plane (202) breaks up into (201) and (211) planes indicating structural transition from orthorhombic with cell parameters as a = 3.896 , b = 5.4886 and c = 7.795 to monoclinic with cell parameters as a = 3.872 , b = 5.4286 and c = 7.8015 and = 88.69 (Fig. 4), showing agreement with the results of HPMssbauer spectroscopy at same pressure. All the above points suggest that pressure generates the uniaxial stress which reorients the grain/grain boundaries in the pressure range of 0.60.9 GPa in a particular direction parallel to ac-plane (easy axis of pressurization). Further increment of pressure gives a structural transition at 3.6 GPa from orthorhombic to monoclinic. Nano-crystalline perovskites La0.8Sr0.2Mn0.8Fe0.2O3 as a function of pressure up to 10 GPa show sudden increase in isomer shift at 0.52 GPa indicating the transformation from Fe4+ to Fe3+ due to transfer of eg electrons from ligand to iron 3 d level under pressure. Second transition is seen at 3.7 GPa where only Fe3+ is distributed with single kind of environment. These phase-transition were accompanied by structural transition seen in HPXRD at 0.6 and 3.6GPa respectively. Transition at 0.6GPa were explained by the reorientation of grain/grain boundaries in a particular direction, while at 3.6 GPa the structure transforms from orthorhombic to monoclinic.