Low-temperature high magnetic field powder x-ray diffraction setup for field-induced structural phase transition studies from 2 to 300 K and at 0 to 8-T field.

A low-temperature and high magnetic field powder x-ray diffractometer (XRD) has been developed at UGC-DAE CSR (UGC: University Grant Commission, DAE: Department of Atomic Energy, and CSR: Consortium for scientific research), Indore, India. The setup has been developed around an 18 kW rotating anode x-ray source delivering Cu-Kα x-rays coming from a vertical line source. It works in a symmetric θ-2θ parallel beam geometry. It consists of a liquid helium cryostat with an 8 T split-pair Nb-Ti superconducting magnet comprising two x-ray windows each covering an angular range of 65°. This is mounted on a non-magnetic type heavy duty goniometer equipped with all necessary motions along with data collection accessories. The incident x-ray beam has been made parallel using a parabolic multilayer mirror. The scattered x-ray is detected using a NaI detector through a 0.1° acceptance solar collimator. To control the motions of the goniometer, a computer programme has been developed. The wide-angle scattering data can be collected in a range of 2°-115° of 2θ with a resolution of ∼0.1°. The whole setup is tightly shielded for the scattered x-rays using a lead hutch. The functioning of the goniometer and the artifacts arising possibly due to the effect of stray magnetic field on the goniometer motions, on the x-ray source, and on the detector have been characterized by collecting powder XRD data of a National Institute of Standards and Technology certified standard reference material LaB6 (SRM-660b) and Si powder in zero-field and in-field conditions. Occurrence of field induced structural-phase transitions has been demonstrated on various samples like Pr0.5Sr0.5MnO3, Nd0.49Sr0.51MnO3-δ and La0.175Pr0.45Ca0.375MnO3 by collecting data in zero field cool and field cool conditions.

Neutron diffraction evidence for kinetic arrest of first order magneto-structural phase transitions in some functional magnetic materials.

Neutron diffraction measurements, performed in the presence of an external magnetic field, have been used to show structural evidence for the kinetic arrest of the first order phase transition from (i) the high temperature austenite phase to the low temperature martensite phase in the magnetic shape memory alloy Ni37Co11Mn42.5Sn9.5, (ii) the higher temperature ferromagnetic phase to the lower temperature antiferromagnetic phase in the half-doped charge ordered compound La0.5Ca0.5MnO3 and (iii) the formation of glass-like arrested states in both compounds. The cooling and heating under unequal fields protocol has been used to establish phase coexistence of metastable and equilibrium states, and also to demonstrate the devitrification of the arrested metastable states in the neutron diffraction patterns. We also explore the field­temperature dependent kinetic arrest line TK(H), through the transformation of the arrested phase to the equilibrium phase. This transformation has been observed isothermally in reducing H, as also on warming in constant H. TK is seen to increase as H increases in both cases, consistent with the low-T equilibrium phase having lower magnetization.

Low temperature high magnetic field 57Fe Mössbauer study of kinetic arrest in Ta doped HfFe2.

Low temperature high magnetic field (57)Fe Mössbauer measurements were carried out on the inter-metallic compound Hf0.77Ta0.23Fe2 by following novel paths in H-T space. The ferromagnetic (FM) fraction at 5 K and zero magnetic field is shown to depend on the cooling field, i.e., the higher the field is, the higher the FM fraction is. Mössbauer spectra collected in the presence of a 4 T magnetic field show that the antiferromagnetic (AFM) spins are canted with respect to the applied magnetic field and hence contribute to the total bulk magnetization in this compound. The data also show an induced magnetic moment even at the 2a site of the AFM phase. Mössbauer spectra collected using the CHUF (cooling and heating in un-equal magnetic fields) protocol show a reentrant transition when the sample is cooled in zero field and measured during warming in 4 T, showing the FM state as the equilibrium state. This work is the first microscopic experimental evidence for the de-vitrification of the kinetically arrested magnetic state.

Concentration dependence in kinetic arrest of the first-order magnetic transition in Ta doped HfFe2.

Magnetic behavior of the pseudo-binary alloy Hf(1-x)Ta(x)Fe(2) has been studied, for which the zero-field ferromagnetic (FM) to antiferromagnetic (AFM) transition temperature is tuned near to T = 0 K. Our studies show that such composition lies around x = 0.230. Detailed magnetization studies on x = 0.225, 0.230 and 0.235 show thermomagnetic irreversibility at low temperature due to kinetic arrest of the first-order AFM-FM transition. All three compositions studied show a reentrant transition in the zero-field-cooled warming curve and non-monotonic variation of the upper critical field. The region in H-T space where these features of kinetic arrest manifest themselves increases with increasing Ta concentration.

The metal-insulator transition in nanocrystalline Pr0.67Ca0.33MnO3: the correlation between supercooling and kinetic arrest.

The transition and hysteresis widths of a disorder broadened first order magnetic transition vary in H-T space which influences the co-existing phase fraction at low temperature arising due to kinetic arrest of the first order transition. We explored the role of change in the relative width of the supercooling/superheating band and kinetic arrest band for a ferromagnetic metallic to antiferromagnetic insulating transition. It is shown that for a correlated kinetic arrest and supercooling bands, the topology of the devitrification curves (or transformation across the (H(K),T(K)) band during warming) changes with the change in the relative width of these two bands. In addition to this, for a broader kinetic arrest band, the transformation temperature across the superheating band under constant H now depends on the arrested phase fraction. These predictions have been tested on nanocrystalline Pr(0.67)Ca(0.33)MnO(3), which is known to show a large variation in hysteresis width in H-T space. This is the first report where correlation between the kinetic arrest band and the supercooling band has been shown experimentally, in contrast to the universal observation of anticorrelation reported so far.

Magnetic glass in shape memory alloy: Ni45Co5Mn38Sn12.

The first order martensitic transition in the ferromagnetic shape memory alloy Ni(45)Co(5)Mn(38)Sn(12) is also a magnetic transition and has a large field induced effect. While cooling in the presence of a field this first order magnetic martensite transition is kinetically arrested. Depending on the cooling field, a fraction of the arrested ferromagnetic austenite phase persists down to the lowest temperature as a magnetic glassy state, similar to the one observed in various intermetallic alloys and in half doped manganites. A detailed investigation of this first order ferromagnetic austenite (FM-A) to low magnetization martensite (LM-M) state transition as a function of temperature and field has been carried out by magnetization measurements. Extensive cooling and heating in unequal field (CHUF) measurements and a novel field cooled protocol for isothermal MH measurements (FC-MH) are utilized to investigate the glass like arrested states and show a reverse martensite transition. Finally, we determine a field-temperature (HT) phase diagram of Ni(45)Co(5)Mn(38)Sn(12) from various magnetization measurements which brings out the regions where thermodynamic and metastable states coexist in the HT space, clearly depicting this system as a 'magnetic glass'.

Tuning the phase transition dynamics by variation of cooling field and metastable phase fraction in Al doped Pr0.5Ca0.5MnO3.

We report the effect of field, temperature and thermal history on the time dependence in resistivity and magnetization in the phase separated state of Al doped Pr(0.5)Ca(0.5)MnO(3). The rate of time dependence in resistivity is much higher than that of magnetization and it exhibits a different cooling field dependence due to percolation effects. Our analysis shows that the time dependence in physical properties depends on the phase transition dynamics, which can be effectively tuned by variation of temperature, cooling field and metastable phase fraction. The phase transition dynamics can be broadly divided into the arrested and unarrested regimes, and in the arrested regime this dynamics is mainly determined by time taken in the growth of critical nuclei. An increase in cooling field and/or temperature shifts this dynamics from the arrested to unarrested regime, and in this regime, this dynamics is determined by the thermodynamically allowed rate of formation of critical nuclei, which in turn depends on the cooling field and available metastable phase fraction. At a given temperature, a decrease in metastable phase fraction shifts the crossover from arrested to unarrested regimes towards lower cooling field. It is rather significant that in spite of the metastable phase fraction calculated from resistivity being somewhat off that of magnetization, their cooling field dependence exhibits a striking similarity, which indicates that the dynamics in arrested and unarrested regimes are so different that it comes out vividly provided that the measurements are performed around the percolation threshold.

First-order antiferro-ferromagnetic transition in Fe(49)(Rh(0.93)Pd(0.07))(51) under simultaneous application of magnetic field and external pressure.

A magnetic field-pressure-temperature (H-P-T) phase diagram for first-order antiferromagnetic (AFM) to ferromagnetic (FM) transitions in Fe(49)(Rh(0.93)Pd(0.07))(51) has been constructed using resistivity measurements under simultaneous application of magnetic field (up to 8 T) and pressure (up to 20 kbar). The temperature dependence of resistivity (ρ-T) shows that the width of the transition and the extent of hysteresis decreases with pressure and increases with magnetic field. By exploiting opposing trends of dT(N)/dP and dT(N)/dH (where T(N) is the first-order transition temperature), the relative effects of temperature, magnetic field and pressure on disorder-broadened first-order transitions has been studied. For this, a set of H and P values are chosen for which T(N)(H(1),P(1)) = T(N)(H(2),P(2)). Measurements for such combinations of H and P show that the temperature dependence of resistivity is similar, i.e. the broadening (in temperature) of transition as well as the extent of hysteresis remains independent of H and P. Isothermal magnetoresistance measurements under various constant pressures show that even though the critical field required for AFM-FM transition depends on applied pressure, the extent of hysteresis as well as transition width (in magnetic field) remains constant with varying pressure.

Field dependence of temperature induced irreversible transformations of magnetic phases in Pr(0.5)Ca(0.5)Mn(0.975)Al(0.025)O(3) crystalline oxide.

Glass-like arrest has recently been reported in various magnetic materials. As in structural glasses, the kinetics of a first order transformation is arrested while retaining the higher entropy phase as a non-ergodic state. We show visual mesoscopic evidence of the irreversible transformation of the arrested antiferromagnetic-insulating phase in Pr(0.5)Ca(0.5)Mn(0.975)Al(0.025)O(3) to its equilibrium ferromagnetic-metallic phase with an isothermal increase of magnetic field, similar to its iso-field transformation on warming. The magnetic field dependence of the non-equilibrium to equilibrium transformation temperature is shown to be governed by Le Chatelier's principle.

Effect of strain on the phase separation and devitrification of the magnetic glass state in thin films of La(5/8-y)Pr(y)Ca(3/8)MnO(3) (y = 0.45).

We present our study of the effect of substrate induced strain on La(5/8-y)Pr(y)Ca(3/8)MnO(3) (y = 0.45) thin films grown on LaAlO(3), NdGaO(3) and SrTiO(3) substrates that show large scale phase separation. It is observed that unstrained films grown on NdGaO(3) behave quite similarly to bulk material but the strained films grown on SrTiO(3) show melting of the insulating phase to the metallic phase at low temperatures. However, the large scale phase separation and metastable glass-like state is observed in all the films despite differences in substrate induced strain. The measurements of resistivity as a function of temperature under a cooling and heating in unequal field (CHUF) protocol elucidate the presence of a glass-like metastable phase generated due to kinetic arrest of the first order transformation in all the films. Like structural glasses, these magnetic glass-like phases show evidence of devitrification of the arrested charge order antiferromagnetic insulator (CO-AFI) phase to the equilibrium ferromagnetic metallic (FMM) phase with isothermal increase of magnetic field and/or iso-field warming. These measurements also clearly show the equilibrium ground state of this system to be FMM and the metastable glass-like phase to be AFI phase.

Conversion of a glassy antiferromagnetic-insulating phase to an equilibrium ferromagnetic-metallic phase by devitrification and recrystallization in Al substituted Pr(0.5)Ca(0.5)MnO(3).

We show that Pr(0.5)Ca(0.5)MnO(3) with 2.5% Al substitution and La(0.5)Ca(0.5)MnO(3) (LCMO) exhibit qualitatively similar and visibly anomalous M-H curves at low temperature. Magnetic field causes a broad first order but irreversible antiferromagnetic (AF)-insulating (I) to ferromagnetic (FM)-metallic (M) transition in both and gives rise to a soft FM state. However, the low temperature equilibrium state of Pr(0.5)Ca(0.5)Mn(0.975)Al(0.025)O(3) (PCMAO) is FM-M whereas that of LCMO is AF-I. In both systems the respective equilibrium phase coexists with the other phase with contrasting order, which is not in equilibrium, and the cooling field can tune the fractions of the coexisting phases. It is shown earlier that the coexisting FM-M phase behaves like 'magnetic glass' in LCMO. Here we show from specially designed measurement protocols that the AF-I phase of PCMAO has all the characteristics of magnetic glassy states. It devitrifies on heating and also recrystallizes to an equilibrium FM-M phase after annealing. This glass-like AF-I phase also shows a similar intriguing feature observed in FM-M magnetic glassy state of LCMO, that when the starting coexisting fraction of glass is larger, successive annealing results in a larger fraction of the equilibrium phase. This similarity between two manganite systems with contrasting magnetic orders of respective glassy and equilibrium phases points to a possible universality.

First order magnetic transition in doped CeFe2 alloys: phase coexistence and metastability.

First order ferromagnetic (FM) to antiferromagnetic (AFM) phase transition in doped CeFe2 alloys is studied with the micro-Hall probe technique. Clear visual evidence of magnetic phase coexistence on micrometer scales and the evolution of this phase coexistence as a function of temperature, magnetic field, and time across the first order FM-AFM transition is presented. Such phase coexistence and metastability arise as a natural consequence of an intrinsic disorder-influenced first order transition. The generality of these phenomena involving other classes of materials is discussed.