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Dielectric and magnetic properties of FE- and Nb-doped CaCu3Ti4O12

Proposed for publication in Physical Review B.

Grubbs, Robert K.; Venturini, Eugene L.; Clem, Paul G.; Richardson, Jacob J.; Tuttle, Bruce T.; Samara, George A.

Detailed studies of the properties of ceramic CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) have clarified the physics of this interesting material and revealed several features not reported before. The dielectric relaxational properties of CCTO are explained in terms of a capacitive-layer model, as for an inhomogeneous semiconductor, consisting of semiconducting grains and insulating grain boundaries as also concluded by others. The kinetics of the main [low-temperature (T)] relaxation reveal that two different thermally activated processes in CCTO grains control the dynamics. A likely candidate defect responsible for the two processes is the oxygen vacancy which is a double donor. A higher-T relaxation is determined by grain boundary conduction. Both Nb and Fe doping lowered both the apparent dielectric constant {var_epsilon}{prime} and the dielectric loss, but increased Fe doping led to more dramatic effects. At 3 at.% Fe doping, the anomalous {var_epsilon}{prime}(T) response was removed, making the CCTO an intrinsic, very-low-loss dielectric. The intrinsic {var_epsilon}{prime}({approx}75) and its T dependence are measured and shown to be largely determined by a low-lying soft TO phonon. At low T, cubic CCTO transforms into an antiferromagnetic phase at T{sub N} = 25 K. T{sub N} is essentially independent of Nb doping (up to 4 at.%) and of hydrostatic pressure (up to {approx}7 kbar), but decreases significantly with Fe doping. Analysis of the high-T dependence of the magnetic susceptibility provided insight into the role of Fe as a dopant. Finally, an {var_epsilon}{prime}(T) anomaly associated with the onset of antiferromagnetic order has been discovered, providing evidence for coupling between the polarization and sublattice magnetization. The possible origin of this coupling is discussed.

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The ferroelectric and relaxor properties of Pb(Sc0.5Nb0.5)O3 : influence of pressure and biasing electric field

Proposed for publication in Physical Review B.

Venturini, Eugene L.; Grubbs, Robert K.; Samara, George A.

The influences of hydrostatic pressure and biasing electric field on the dielectric properties and phase behavior of a single crystal of the perovskite compound Pb(Sc{sub 0.5}Nb{sub 0.5})O{sub 3}, (PSN) have been investigated. On cooling from high temperatures, the crystal first enters a relaxor (R) state and then spontaneously transforms to a ferroelectric (FE) phase at a temperature, T{sub c}, substantially below the peak temperature, T{sub m}, in the dielectric susceptibility. Based on earlier work on ceramic samples, this behavior suggests substantial chemical (Sc and Nb) disorder at the B sites. Pressure enhances the R state with strong indications that the FE phase should vanish at a pressure somewhat higher than the highest pressure reached in the experiments, making the R state the ground state of the crystal at reduced volume. A significant feature of the temperature (T)-pressure (P) phase diagram is the finding that the T{sub c}(P) phase line should terminate at a pressure between 10 and 15 kbar in a manner akin to a critical point; however, in the case of PSN this feature represents a FE-to-R crossover. Such behavior suggests that a path can be defined that takes the crystal from the FE phase to the R state without crossing a phase boundary. A biasing electric field favors the FE phase over the R state, and the results indicate that the R state vanishes at 5 kV/cm. The magnitudes of both the high T Curie-Weiss constant, C, and the change in entropy (or latent heat) at T{sub c} are found to be comparable to those of simple displacive perovskite oxides such as BaTiO{sub 3} and PbTiO{sub 3}.

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Using triaxial magnetic fields to create high susceptibility particle composites

Physical Review E - Statistical, Nonlinear, and Soft Matter Physics

Martin, James E.; Venturini, Eugene L.; Gulley, Gerald L.; Williamson, Jonathan

The use of triaxial magnetic fields to create a variety of isotropic and anisotropic magnetic particle/polymer composites with significantly enhanced magnetic susceptibilities was analyzed. It was shown that a rich variety of structures can be created because both the field amplitudes and frequencies can be varied. It was found that the susceptibility anisotropy of these composites can be controlled over a wide range by judicious adjustment of the relative field amplitudes. The results show that with coherent particle motions, magnetostatic energies that are quite close to the ground state can be achieved.

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Pressure as a probe of the physics of 18O - substituted SrTiO3

Proposed for publication in Physical Review B.

Venturini, Eugene L.; Venturini, Eugene L.; Samara, George A.

Studies of the dielectric properties and phase behavior of an {sup 18}O-substituted SrTiO{sub 3} (>97% {sup 18}O), or STO-18, crystal at 1 bar and as functions of hydrostatic pressure and applied dc biasing electric field have shed much light on the mechanism of the {sup 18}O-induced ferroelectric transition in this material. Dielectric measurements reveal an equilibrium phase transition (T{sub c} {approx_equal} 24K at 1 bar) and an enhancement of the static dielectric constant {var_epsilon} over that of normal (i.e., {sup 16}O) SrTiO{sub 3}, or STO-16, over a large temperature range above T{sub c}. This enhancement is quantitatively shown to be attributed to additional softening of the ferroelectric soft-mode frequency ({omega}{sub s}) of STO-16, in agreement with lattice dynamic calculations. Thus, in STO-18, two effects due to the heavier mass of {sup 18}O conspire to induce the transition: (i) this additional softening of {omega}{sub s} and (ii) damping of quantum fluctuations. Pressure lowers T{sub c} at the large initial rate of 20 K/kbar and completely suppresses the ferroelectric state leading to a quantum paraelectric state at 0.7 kbar, confirming earlier results. Very large effects of a biasing dc electric fields on the peak temperature and {var_epsilon} are also observed in the quantum regime reflecting the small characteristic energies of the system. The results also reveal a dielectric relaxation process near 10 K with interesting properties. The implications of all the results on our understanding of the physics of STO-18 are discussed.

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Synthesis of highly magnetic iron nanoparticles suitable for field-structuring using a b-diketone surfactant

Proposed for publication in Nano Letters.

Huber, Dale L.; Huber, Dale L.; Venturini, Eugene L.; Martin, James E.; Provencio, P.N.

We describe the synthesis of highly magnetic iron nanoparticles using a novel surfactant, a {beta}-diketone. We have produced 6 nm iron nanoparticles with an unusually high saturation magnetization of more than 80% the value of bulk iron. Additionally, we measured a particle susceptibility of 14 (MKS units), which is far above the value possible for micron-scale spherical particles. These properties will allow for formation of composites that can be highly structured by magnetic fields.

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Magnetic response of dilute cobalt nanoparticles in an organic matrix : the effects of aging and interface chemistry

Proposed for publication in Physical Review Letters.

Wilcoxon, Jess P.; Wilcoxon, Jess P.; Venturini, Eugene L.; Provencio, P.N.

We report studies of the magnetic response of dilute frozen solutions of nanocrystalline Co particles grown in inverse micelles. Crystalline nanoclusters which initially exhibit only a small fraction of the bulk saturation moment restructure in solution without any change in cluster size or blocking temperature over a period of {approx}30-60 days, finally yielding a moment/atom which exceeds that of bulk Co. The saturation magnetism maintains its enhanced value for temperatures up to the melting point of the solvent matrix, but is strongly dependent on surface active additives and molecular oxygen.

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Giant magnetic susceptibility enhancement in field-structured dipolar nanocomposites

Proposed for publication in Physical Review B.

Martin, James E.; Martin, James E.; Venturini, Eugene L.; Huber, Dale L.

We demonstrate through experiment and simulation that when mono-domain Fe nanoparticles are formed into chains by the application of a magnetic field, the susceptibility of the resulting structure is greatly enhanced (11.4-fold) parallel to the particle chains and is much larger than transverse to the chains. Simulations show that this significant enhancement is expected when the susceptibility of the individual particles approaches 5 in MKS units, and is due to the spontaneous magnetization of individual particle chains, which occurs because of the strong dipolar interactions. This large enhancement is only possible with nanoparticles, because demagnetization fields limit the susceptibility of a spherical multi-domain particle to 3 (MKS). Experimental confirmation of the large susceptibility enhancement is presented, and both the enhancement and the susceptibility anisotropy are found to agree with simulation. The specific susceptibility of the nanocomposite is 54 (MKS), which exceeds the highest value we have obtained for field-structured composites of multi-domain particles by a factor of four.

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The Dielectric Properties and Phase Transitions of [Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}]{sub 0.905} (PbTiO{sub 3}){sub 0.095}: Influence of Pressure

Physical Review Journal

Samara, George A.; Venturini, Eugene L.

Studies of the influences of temperature, hydrostatic pressure, dc biasing field and frequency on the dielectric constant ({epsilon}{prime}) and loss (tan {delta}) of single crystal [pb (Zn{sub 1/3}Nb{sub 2/3})O{sub 3}]{sub 0.905} (PbTiO{sub 3}){sub 0.095}, or PZN-9.5PT for short, have provided a detailed view of the ferroelectric (FE) response and phase transitions of this technologically important material. While at 1 bar, the crystal exhibits on cooling a cubic-to-tetragonal FE transition followed by a second transition to a rhombohedral phase, pressure induces a FE-to-relaxer crossover, the relaxer phase becoming the ground state at pressures {ge}5 kbar. Analogy with earlier results suggests that this crossover is a common feature of compositionally-disordered soft mode ferroelectrics and can be understood in terms of a decrease in the correlation length among polar domains with increasing pressure. Application of a dc biasing electric field at 1 bar strengthens FE correlations, and can at high pressure re-stabilize the FE response. The pressure-temperature-electric field phase diagram was established. In the absence of dc bias the tetragonal phase vanishes at high pressure, the crystal exhibiting classic relaxor behavior. The dynamics of dipolar motion and the strong deviation from Curie-Weiss behavior of the susceptibility in the high temperature cubic phase are discussed.

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Precision formed micro magnets: LDRD project summary report

Christenson, Todd R.; Garino, Terry J.; Venturini, Eugene L.

A microfabrication process is described that provides for the batch realization of miniature rare earth based permanent magnets. Prismatic geometry with features as small as 5 microns, thicknesses up through several hundred microns and with submicron tolerances may be accommodated. The processing is based on a molding technique using deep x-ray lithography as a means to generate high aspect-ratio precision molds from PMMA (poly methyl methacrylate) used as an x-ray photoresist. Subsequent molding of rare-earth permanent magnet (REPM) powder combined with a thermosetting plastic binder may take place directly in the PMMA mold. Further approaches generate an alumina form replicated from the PMMA mold that becomes an intermediate mold for pressing higher density REPM material and allows for higher process temperatures. Maximum energy products of 3--8 MGOe (Mega Gauss Oersted, 1 MGOe = 100/4{pi} kJ/m{sup 3}) are obtained for bonded isotropic forms of REPM with dimensions on the scale of 100 microns and up to 23 MGOe for more dense anisotropic REPM material using higher temperature processing. The utility of miniature precision REPMs is revealed by the demonstration of a miniature multipole brushless DC motor that possesses a pole-anisotropic rotor with dimensions that would otherwise prohibit multipole magnetization using a multipole magnetizing fixture at this scale. Subsequent multipole assembly also leads to miniaturized Halbach arrays, efficient magnetic microactuators, and mechanical spring-like elements which can offset miniaturized mechanical scaling behavior.

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Pressure-induced crossover from long-to-short-range order in [Pb(Zn{sub 1/3})Nb{sub 2/3}O{sub 3}]{sub 0.905}(PbTiO{sub 3}){sub 0.095} single crystal

Applied Physics Letters

Samara, George A.; Venturini, Eugene L.

A pressure-induced crossover from normal Ferroelectric-to-Relaxer behavior has been observed in single crystal [Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3}]{sub 0.905}(PbTiO{sub 3}){sub 0.0095}, or PZN - 9.5% PT. Analogy with similar observations for other perovskites indicates that this crossover is a general feature of compositionally-disordered soft mode ferroelectrics. The Pressure-Temperature phase diagram has been also determined.

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20 Results
20 Results