arXiv subjects
Publications and source records attributed to K. R. Priolkar.
The L-arginine mixed potassium dihydrogenphosphate (KDP) crystal reported by Saravanan et al Indian J Pure App Phys 51 (2013) 254, is a dubious crystal. The reported unit cell parameters contradict the definition of the tetragonal crystal system.
A study investigating the effect of Sn substitution on the magnetocaloric properties of Mn$ _{3} $Ga$ _{(1-x)} $Sn$ _{x} $C compounds reveals that nature of the MCE has a strong dependence on the nature of the magnetic ordering. For small amounts of Sn ($ x\leq0.2 $) the MCE is of the inverse type wherein an increase in the applied field beyond 5T gives rise to a table like temperature dependence of the entropy due to a coupling between the first order FM - AFM transition and the field induced AFM - FM transition. Replacement of Ga by larger concentrations of Sn ($ x\geq0.71 $) $(ΔS_M)$ results in a change of the MCE to a conventional type with very little variation in the position of $(ΔS_M)_{max}$ with increasing magnetic field. This has been explained to be due to the local strain introduced by A site ions (Ga/Sn) which affect the magnetostructural coupling in these compounds.
In this paper we attempt to understand the different nature of first order magnetic transformation in Mn$_3$SnC as compared to that in Mn$_3$GaC. The transformation in Mn$_3$SnC is close to room temperature (T$_t \approx$ 280K) and is associated with a large change in magnetic entropy that makes it a suitable candidate for applications in ferroic cooling. Using a combination of x-ray and neutron diffraction and x-ray absorption fine structure (XAFS) spectroscopy we infer that the magnetic ground state consisting of antiferromagnetic and ferromagnetic Mn atoms is due to structural distortions present in Mn$_6$C octahedra.
Cr$^{3+}$ doped spinel compounds AB$_2$O$_4$ with A=Zn, Mg and B=Ga, Al exhibit a long near infrared persistent luminescence when excited with UV or X-rays. In addition, persistent luminescence of ZnGa$_2$O$_4$ and to a lesser extent MgGa$_2$O$_4$, can also be induced by visible light excitation via $^4$A$_2$ $ \rightarrow $ $^4$T$_2$ transition of Cr$^{3+}$, which makes these compounds suitable as biomarkers for in vivo optical imaging of small animals. We correlate this peculiar optical property with the presence of antisite defects, which are present in ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. By using X-ray absorption fine structure (XAFS) spectroscopy, associated with electron paramagnetic resonance (EPR) and optical emission spectroscopy, it is shown that an increase in antisite defects concentration results in a decrease in the Cr-O bond length and the octahedral crystal field energy. A part of the defects are in the close environment of Cr$^{3+}$ ions, as shown by the increasing strain broadening of EPR and XAFS peaks observed upon increasing antisite disorder. It appears that ZnAl$_2$O$_4$, which exhibits the largest crystal field splitting of Cr$^{3+}$ and the smallest antisite disorder, does not show considerable persistent luminescence upon visible light excitation as compared to ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. These results highlight the importance of Cr$^{3+}$ ions with neighboring antisite defects in the mechanism of persistent luminescence exhibited by Cr$^{3+}$ doped AB$_2$O$_4$ spinel compounds.
The structure, magnetic and martensitic properties of Fe doped Ni-Mn-In magnetic shape memory alloys have been studied by differential scanning calorimetry, magnetization, resistivity, X-ray diffraction (XRD) and EXAFS. While Ni$_{2}$MnIn$_{1-x}$Fe$_{x}$ ($0 \le x \le 0.6$) alloys are ferromagnetic and non martensitic, the martensitic transformation temperature in Ni$_{2}$Mn$_{1.5} $In$_{1-y}$Fe$_{y}$ and Ni$_{2}$Mn$ _{1.6} $In$_{1-y}$Fe$_{y}$ increases for lower Fe concentrations ($y \le 0.05$) before decreasing sharply for higher Fe concentrations. XRD analysis reveals presence of cubic and tetragonal structural phases in Ni$_{2}$MnIn$_{1-x}$Fe$_{x}$ at room temperature with tetragonal phase content increasing with Fe doping. Even though the local structure around Mn and Ni in these Fe doped alloys is similar to martensitic Mn rich Ni-Mn-In alloys, presence of ferromagnetic interactions and structural disorder induced by Fe affect Mn-Ni-Mn antiferromagnetic interactions resulting in suppression of martensitic transformation in these Fe doped alloys.
Neutron diffraction studies as a function of temperature on solid solutions of MnSe and MnTe in the Se rich region are presented. Interestingly as Te is doped in MnSe, the structural transformation to NiAs phase diminishes, both in terms of \% fraction of compound as well as in terms of transition temperature. In MnTe$_{0.3}$Se$_{0.7}$, the NaCl to NiAs phase transformation occurs at about 40K and although it is present at room temperature in MnTe$_{0.5}$Se$_{0.5}$, its volume fraction is only about 10\% of the total volume of sample. The magnetic ordering temperature of the cubic phase decreases with increasing Te content while the hexagonal phase orders at the same temperature as in MnSe. Anomalies in thermal evolution of lattice parameters at magnetic ordering as well as structural transition temperatures indicate presence of magnetostructural coupling in these compounds.
Temperature (12K $\le$ T $\le$ 300K) dependent extended X-ray absorption fine structure (EXAFS) studies at the Fe K edge in FeSe$_{1-x}$Te$_x$ (x = 0, 0.5 and 1.0) compounds have been carried out to understand the reasons for increase in T$_C$ upon Te doping in FeSe. While local distortions are present near superconducting onset in FeSe and FeSe$_{0.5}$Te$_{0.5}$, they seem to be absent in non superconducting FeTe. Of crucial importance is the variation of anion height. In FeSe$_{0.5}$Te$_{0.5}$, near superconducting onset, the two heights, $h_{Fe-Se}$ and $h_{Fe-Te}$ show a nearly opposite behaviour. These changes indicate a possible correlation between Fe-chalcogen hybridization and the superconducting transition temperature in these Fe-chalcogenides.
EXAFS studies at the As K edge as a function of temperature have been carried out in SmFeAsO$_{1-x}$F$_x$ ($x$ = 0 and 0.2) compounds to understand the role of local structural distortions superconductivity observed in F doped compound. A significant correlation between thermal variation of local structural parameters like anion height and superconducting onset is found in the fluorinated compound. Such a variation in anion height is absent in non-superconducting compound. Increase in Fe-As bond distance just below superconducting onset temperature indicates a similarity in distortions observed in high T$_C$ cuprates and these Fe based superconductors.
The magnetic properties of the Mn$_3$Ga$_{(1-x)}$Sn$_x$C, 0 $\le$ x $\le$ 1 antiperovskite compounds have been investigated in detail. Though all compounds of this series crystallize in a cubic structure, the Ga rich (x $\le$ 0.2) compounds transform, via a first order transformation, to an antiferromagnetic ground state and the Sn rich (x $\ge$ 0.8) compounds exhibit dominant ferromagnetic interactions at low temperature. In the intermediate range (0.4 $\le$ x $\le$ 0.7) co-existence of ferromagnetic and antiferromagnetic interactions can be seen. The results have been explained to be due to growth of ferromagnetic sub-lattice at the expense of antiferromagnetic sub-lattice with increasing Sn concentration in Mn$_3$Ga$_{(1-x)}$Sn$_x$C. This growth occurs to a point where the first-order transition is altered from a ferromagnetic - antiferromagnetic type in Ga rich compounds to a paramagnetic - ferrimagnetic type in Mn$_3$SnC.
Effect of carbon content on magnetostructural transformation in antiperovskites of the type Mn$_3$GaC$_x$ ($x$ = 0.8, 1.0 and 1.05) has been investigated. It is found that, increase in carbon content changes the ground state from ferromagnetic metallic ($x$ = 0.8) to antiferromagnetic semiconducting ($x$ = 1.05) type. This has been attributed to localization of itinerant Mn $3d$ electrons due to increased Mn$3d$ - C$2p$ hybridization. Such a hybridization strengthens Mn-C-Mn antiferromagnetic interactions over Mn-Mn ferromagnetic interactions. Further, magnetic field can be used as a tool to modulate the relative strengths of these ferromagnetic and antiferromagnetic interactions thereby affecting the nature and strength of magnetocaloric properties.
The magnetic properties of Mn$_{2}$Ni$_{(1+x)}$In$_{(1-x)}$ ($x$ = 0.5, 0.6, 0.7) and Mn$_{(2-y)}$Ni$_{(1.6+y)}$In$_{0.4}$ ($y$ = -0.08, -0.04, 0.04, 0.08) shape memory alloys have been studied. Magnetic interactions in the martensitic phase of these alloys are found to be quite similar to those in Ni$_2$Mn$_{(1+x)}$In$_{(1-x)}$ type alloys. Doping of Ni for In not only induces martensitic instability in Mn$_2$NiIn type alloys but also affects magnetic properties due to a site occupancy disorder. Excess Ni preferentially occupies X sites forcing Mn to the Z sites of X$_2$YZ Heusler composition resulting in a transition from ferromagnetic ground state to a state dominated by ferromagnetic Mn(Y) - Mn(Y) and antiferromagnetic Mn(Y)-Mn(Z) interactions. These changes in magnetic ground state manifest themselves in observation of exchange bias effect even in zero field cooled condition and virgin magnetization curve lying outside the hysteresis loop.
Magnetism in Ni-Mn-Z (Z = Ga,In,Sn,Sb) Heusler alloys has so far been predominantly attributed to Rudermann-Kittel-Kasuya-Yoshida type interactions between Mn atoms. We investigate magnetic interactions in one such alloy, Ni$_{2}$Mn$_{1.4}$In$_{0.6}$ and attempt to explain the origin of antiferromagnetic (AFM) interactions that coexist with ferromagnetic ones. Through the combination of x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD), we find that Ni plays an important role along with Mn in the overall magnetism. A significant hybridization that develops between Mn and Ni orbitals results in a small antiferromagnetic moment at Ni sites. The shift in the XMCD hysteresis loops in the martensitic phase suggests that antiferromagnetism results from superexchange like interactions between Mn atoms mediated by Ni.
The effect of local structure on the magnetic and transport properties of the layered perovskites has been investigated. The samples PrBaCo$_{2}$O$_{5+δ}$, ($δ$ = 0.80 and 0.67) though crystallize in the same 112 type tetragonal structure have different magnetic ground states. Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy has been employed to explain the changes in magnetic interactions based on the rotation and tilting of CoO polyhedra in these oxygen rich double perovskites.
The effect of oxygen content on the magnetic properties of the layered perovskites has been investigated. The samples, PrBaCo$_{2}$O$_{5+δ}$ (0.35 $\leq δ\leq$ 0.80) were prepared by sol-gel method and characterized by X-ray diffraction and DC magnetization. A detailed magnetic phase diagram for PrBaCo$_{2}$O$_{5+δ}$ is presented. It is found that unlike in the case of heavier rare-earths, ferromagnetic interactions are present at all temperatures below Tc and even in the antiferromagnetically ordered phase. Moreover, in compounds with lower oxygen content, short range ferromagnetic interactions are present even above Tc. This dependence of magnetic properties on oxygen content in these layered perovskites has been linked to the changes in polyhedra around the Co ions.
Extended X-ray Absorption Fine Structure (EXAFS) studies on Ni$_{50}$Mn$_{25+x}$In$_{25-x}$ have been carried out at Ni and Mn K edge as a function of temperature. Thermal evolution of nearest neighbor Ni-Mn and Mn-Mn bond distances in the martensitic phase give a clear evidence of a close relation between structural and magnetic degrees of freedom in these alloys. In particular, the study highlights the role of Ni 3d - Mn 3d hybridization in the magnetism of martensitic phase of these alloys.
Infrared absorption study has been carried out on a series of half doped manganites, $La_{0.5}Ca_{0.5-x}Sr_{x}MnO_{3}$ $(0.1\leq x\leq0.5)$, with varying magnetic ground state. The charge ordering transition observed in samples with {\normalsize $x\leq0.3$ is accompanied by a mode at $\sim525cm^{-1}$ in addition to the stretching mode at $615cm^{-1}$ and bending mode at $400cm^{-1}$. Phonon hardening is found to occur below the CE - type antiferromagnetic ordering temperature. The value of the insulating gap decreases on doping with Sr from $727cm^{-1}$ to $615cm^{-1}.$}
The perovskite solid solutions of the type La$_{2x}$Sr$_{2-2x}$Co$_{2x}$Ru$_{2-2x}$O$_{6}$ with 0.25 $\leq$ x $ \leq $ 0.75 have been investigated for their structural, magnetic and transport properties. All the compounds crystallize in double perovskite structure. The magnetization measurements indicate a complex magnetic ground state with strong competition between ferromagnetic and antiferromagnetic interactions. Resistivity of the compounds is in confirmation with hopping conduction behaviour though differences are noted especially for $x$ = 0.4 and 0.6. Most importantly, low field (50Oe) magnetization measurements display negative magnetization during the zero field cooled cycle. X-ray photoelectron spectroscopy measurements indicate presence of Co$^{2+}$/Co$^{3+}$ and Ru$^{4+}$/Ru$^{5+}$ redox couples in all compositions except $x$ = 0.5. Presence of magnetic ions like Ru$^{4+}$ and Co$^{3+}$ gives rise to additional ferromagnetic (Ru-rich) and antiferromagnetic sublattices and also explains the observed negative magnetization.
Effect of Co, Ru and Cu substitution at B and B' sites on the magnetic and transport properties of LaSrCoRuO$_6$ have been investigated. All the doped compositions crystallize in the monoclinic structure in the space group $P2_1/n$ indicating a double perovskite structure. While the magnetization and conductivity increase in Co and Ru doped compounds, antiferromagnetism is seen to strengthen in the Cu doped samples. These results are explained on the basis of a competition between linear Co-O-Ru-O-Co and perpendicular Co-O-O-Co antiferromagnetic interactions and due to formation of Ru-O-Ru ferromagnetic networks.