Evidence for impurity-induced frustration in La2CuO4

Zero-field muon spin rotation and magnetization measurements were performed in La2Cu{1-x}MxO4, for 0<x< 0.12, where Cu2+ is replaced either by M=Zn2+ or by M=Mg2+ spinless impurity. It is shown that while the doping dependence of the sublattice magnetization (M(x)) is nearly the same for both compounds, the N\'eel temperature (T_N(x)) decreases unambiguously more rapidly in the Zn-doped compound. This difference, not taken into account within a simple dilution model, is associated with the frustration induced by the Zn2+ impurity onto the Cu2+ antiferromagnetic lattice. In fact, from T_N(x) and M(x) the spin stiffness is derived and found to be reduced by Zn doping more significantly than expected within a dilution model. The effect of the structural modifications induced by doping on the exchange coupling is also discussed.Comment: 4 pages, 4 figure

Field evolution of the magnetic structures in Er2_2Ti2_2O7_7 through the critical point

We have measured neutron diffraction patterns in a single crystal sample of the pyrochlore compound Er$_2$Ti$_2$O$_7$ in the antiferromagnetic phase (T=0.3\,K), as a function of the magnetic field, up to 6\,T, applied along the [110] direction. We determine all the characteristics of the magnetic structure throughout the quantum critical point at $H_c$=2\,T. As a main result, all Er moments align along the field at $H_c$ and their values reach a minimum. Using a four-sublattice self-consistent calculation, we show that the evolution of the magnetic structure and the value of the critical field are rather well reproduced using the same anisotropic exchange tensor as that accounting for the local paramagnetic susceptibility. In contrast, an isotropic exchange tensor does not match the moment variations through the critical point. The model also accounts semi-quantitatively for other experimental data previously measured, such as the field dependence of the heat capacity, energy of the dispersionless inelastic modes and transition temperature.Comment: 7 pages; 8 figure

Mesoscopic correlations in Tb2Ti2O7 spin liquid

We have studied the spin correlations with $\bf{k}$= ($\frac12$, $\frac12$, $\frac12$) propagation vector which appear below 0.4\, K in \tbti\ spin liquid by combining powder neutron diffraction and specific heat on Tb$_{2+x}$Ti$_{2-x}$O$_{7+y}$ samples with $x$=0, 0.01, -0.01. The $\bf{k}$= ($\frac12$, $\frac12$, $\frac12$) order clearly appears on all neutron patterns by subtracting a pattern at 1.2(1)\,K. Refining the subtracted patterns at 0.07\,K yields two possible spin structures, with spin-ice-like and monopole-like correlations respectively. Mesoscopic correlations involve Tb moments of 1 to 2 \mub\ ordered on a length scale of about 20 \AA. In addition, long range order involving a small spin component of 0.1 to 0.2 \mub\ is detected for the $x$= 0 and 0.01 samples showing a peak in the specific heat. Comparison with previous single crystals data suggests that the ($\frac12$, $\frac12$, $\frac12$) order settles in through nanometric spin textures with dominant spin ice character and correlated orientations, analogous to nanomagnetic twins

Highly efficient and selective extraction of uranium from aqueous solution by a magnetic device: succinyl-ß-cyclodextrin-APTES@maghemite nanoparticles

The removal of radio-elements, notably uranium, from waste-waters is crucial for public health and environmental remediation. To this end, succinyl-ß-cyclodextrin (SßCD) is grafted onto maghemite nanoparticles (NPs) synthesized by the polyol method. The nanocomposite was well characterized. The adsorption of U(VI) by SßCD-APTES@Fe2O3 is pH-dependent with a maximum at pH 6. Adsorption occurs mainly by complex formation and displays a very good selectivity for U(VI) compared to other cations such as Cs+, K+, Na+, Mg2+ and Al3+. The data were plotted according to the Langmuir, Freundlich, Elovich, Temkin and Halsey isotherms. The Langmuir isotherm maximum adsorption capacity (qmax) is 286 mg U g-1 and higher than for other reported sorbents. Moreover, Cs-corrected STEM visualizes the uranium on the NP surface, which is consistent with the Halsey isotherm model for multilayer adsorption. The U(VI) adsorbed on SßCD-APTES@Fe2O3 is easily recovered by magnetic sedimentation and desorption performed in a small volume in order to concentrate the extract. The nanocomposite can be regenerated and re-used at least tenfold

Magnetic properties and crystal field in Pr2Zr2O7

In this work, we revisit the crystal field acting on the non-Kramers Pr3+ ion (4f2) in the quantum spin ice candidate Pr2Zr2O7 using both a standard calculation restricted to the ground spin-orbit multiplet and intermediate coupling states in the full basis of the f 2 configuration. Analysis of the thermal variation of the polycrystal magnetic susceptibility and of the local susceptibilities χ⊥ and χ// determined by means of polarized neutron diffraction experiments reveals that the effective antiferromagnetic exchange is strongly depleted at low temperature with respect to its high-temperature value.We then discuss the influence of crystal field imperfections arising from residual strains, which are especially important for a non-Kramers ion. We find that they are an essential ingredient to account for the very low temperature M(H) magnetization curves, showing that the saturation is not achieved even at 8 T. Furthermore, as possible candidates to qualitatively understand the Curie-like behavior observed below 0.5 K, we discuss the influence of the magnetic hyperfine interaction

Magnetic structure in the spin liquid Tb2_{2}Ti2_{2}O7_{7} induced by a [111] magnetic field: Search for a magnetization plateau

We have studied the field-induced magnetic structures of Tb2Ti2O7 pyrochlore by single-crystal neutron diffraction under a field applied along the [111] axis, up to H=12 T and down to T=40 mK. We refined the magnetic structures with k=0 propagation vector by performing a symmetry analysis in the space group R3¯m, reducing the number of free parameters to three only. The Tb moments gradually reorient towards the field direction, keeping close to a “3-in, 1-out / 1-in, 3-out” spin structure (magnetic space group R3¯m′) in the whole measured field range 0.05–12 T. Our results rule out the “all-in/all-out” structure previously proposed and do not support the existence of a magnetization plateau. We perform a quantitative comparison with mean-field calculations and we propose the presence of a low-temperature dynamic symmetry breaking of the local trigonal symmetry, akin to a dynamic Jahn-Teller effect, i.e., preserving the overall cubic symmetry. We discuss the possible origin of this off-diagonal mixing term in the crystal field Hamiltonian in terms of quadrupole-quadrupole interaction or magnetoelastic effects

Order by Disorder and Energetic Selection of the Ground State in the XY Pyrochlore Antiferromagnet Er2Ti2O7. An Inelastic Neutron Scattering Study

Examples of materials where an "order by disorder" mechanism is at play to select a particular ground state are scarce. It has recently been proposed, however, that the antiferromagnetic XY pyrochlore Er2Ti2O7, reveals a most convincing case of this mechanism. Observation of a spin gap at zone centers has recently been interpreted as a corroboration of this physics. In this paper, we argue, however, that the anisotropy generated by the interaction-induced admixing between the crystal-field ground and excited levels provides for an alternative mechanism. It especially predicts the opening of a spin gap of about 15 micro-eV, which is of the same order of magnitude as the one observed experimentally. We report new high resolution inelastic neutron scattering data which can be well understood within this scenario.Comment: This version corrects a mistake on the numerical values of the exchange couplings $J$ in relation to the published versio

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of α-pinene

Secondary organic aerosol (SOA) were generated from the ozonolysis of α-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM. The real CRI at 525 nm wavelength decreased from 1.43–1.60 (±0.02) to 1.32–1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02–1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state

Maghemite nanoparticles bearing di(amidoxime) groups for the extraction of uranium from wastewaters

Polyamidoximes (pAMD) are known to have strong affinities for uranyl cations. Grafting pAMD onto the surface of functionalized maghemite nanoparticles (MNP) leads to a nanomaterial with high capacities in the extraction of uranium from wastewaters by magnetic sedimentation. A diamidoxime (dAMD) specifically synthesized for this purpose showed a strong affinity for uranyl: Ka = 105 M-1 as determined by Isothermal Titration Calorimetry (nano-ITC). The dAMD was grafted onto the surface of MNP and the obtained sorbent (MNP-dAMD) was characterized. The nanohybrids were afterward incubated with different concentrations of uranyl and the solid phase recovered by magnetic separation. This latter was characterized by zeta-potential measurements, X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Fluorescence spectroscopy (XRF), whereas the supernatant was analyzed by Inductively Coupled Plasma coupled to Mass Spectrometry (ICP-MS). All the data fitted the models of Langmuir, Freundlich and Temkin isotherms very well. These isotherms allowed us to evaluate the efficiency of the adsorption of uranium by MNP-dAMD. The saturation sorption capacity (qmax) was determined. It indicates that MNP-dAMD is able to extract up to 120 mg of uranium per gram of sorbent. Spherical aberration (Cs)-corrected High-Resolution Scanning Transmission Electron Microscopy (HRSTEM) confirmed these results and clearly showed that uranium is confined at the surface of the sorbent. Thus, MNP-dAMD presents a strong potential for the extraction of uranium from wastewaters