Spin-liquid state with precursor ferromagnetic clusters interacting antiferromagnetically in frustrated glassy tetragonal spinel Zn0.8Cu0.2FeMnO4.

Spinels (AB2O4) with magnetic ions occupying only the octahedralBsites have inherent magnetic frustration which inhibits magnetic long-range order (LRO) but may lead to exotic states. Here we report on the magnetic properties of the tetragonal spinel Zn0.8Cu0.2FeMnO4, the tetragonality resulting from the Jahn-Teller active Mn3+ions. X-ray diffraction and x-ray photoelectron spectroscopy of the sample yielded the composition (Zn0.82+Cu0.22+)A[Fe0.42+Fe0.63+Mn3+]BO4‒δ. Analysis of the temperature dependence of magnetization (M), ac magnetic susceptibilities (χ'andχ''), dc susceptibility (χ), heat capacityCp, and neutron diffraction (ND) measurements show complex temperature-dependent short-range order (SRO) but without LRO. The data ofχ vs. Tfits the Curie-Weiss law:χ = C/(T ‒ θ) fromT= 250 K to 400 K withθ≃ 185 K signifying dominant ferromagnetic (FM) coupling with the FM exchange constantJ/kB= 17 K, andC= 3.29 emu K mol‒1Oe‒1yielding an effective magnetic momentµeff= 5.13µBresulting from the high-spin states of Cu2+(Asite) and Fe2+(Bsite), while theBsite trivalent ions Mn3+and Fe3+are in their low-spin states. The extrapolated saturation magnetization obtained from theM vs. Hdata atT= 2 K is explained using the spin arrangement (Cu2+↓)A[Fe2+↑, Fe3+↓, Mn3+↑]Bleading to FM clusters interact antiferromagnetically at low temperatures. Temperature dependence of d(χT)/dTshows the onset of ferrimagnetism below ∼100 K and peaks near 47 K and 24 K. The relaxation timeτobtained from temperature and frequency dependence ofχ″when fit to the power law and Vogel-Fulcher laws confirm the cluster spin-glass (SG) state. The magnetic field dependence of the SG temperatureTSGHfollows the equation:TSGH=TSG01-AH2/ϕwithTSG(0) = 46.6 K,A= 8.6 × 10‒3Oe‒0.593andϕ= 3.37. The temperature dependence of hysteresis loops yields coercivityHC∼ 3.8 kOe at 2 K without exchange-bias, butHCdecreases with increase inTbecoming zero above 24 K, theTSG(H) forH= 800 Oe. Variations ofCpvs. Tfrom 2 K to 200 K inH=0 andH=90 kOe do not show any peak characteristic of LRO. However, after correcting for the lattice contribution, a broad weak peak typically of SRO becomes evident centered around 40 K. ForT< 9 K,Cpvaries asT2; a typical signature of spin-liquids (SLs). Comparison of the ND measurements at 1.7 K and 79.4 K shows absence of LRO. Time dependence of thermo-remanent magnetizationMTRM(t) studies below 9 K reveal weakening of the inter-cluster interaction with increase in temperature. A summary of these results is that in Zn0.8Cu0.2FeMnO4, ferromagnetic clusters interact antiferromagnetically without LRO but producing a cluster SG state atTSG(0) = 46.6 K, followed by SL behavior below 9 K.

Effects of Cu doping on the electronic structure and magnetic properties of MnCo2O4 nanostructures.

Reported here are the results and their analysis from our detailed investigations of the effects of Cu doping ([Formula: see text]) on the electronic structure and magnetic properties of the spinel [Formula: see text]O4. A detailed comparison is given for the [Formula: see text] and [Formula: see text] cases for both the bulk-like samples and nanoparticles. The electronic structure determined from x-ray photoelectron spectroscopy and Rietveld analysis of x-ray diffraction patterns shows the structure to be: ([Formula: see text])A [Formula: see text] [Formula: see text] [Formula: see text]]B [Formula: see text] i.e. [Formula: see text] substitutes for [Formula: see text] on the octahedral B-sites. For the bulk samples, the ferrimagnetic [Formula: see text] K for [Formula: see text] is lowered to [Formula: see text] K for the [Formula: see text] sample, this decrease being due to the effect of Cu doping. For the nanosize [Formula: see text] ([Formula: see text]) sample, the lower [Formula: see text] K ([Formula: see text] K) is observed using [Formula: see text] analysis, this lowering being due to finite size effects. For [Formula: see text], fits of dc paramagnetic susceptibility data of [Formula: see text] versus T in nanosize samples to the Néel expression are used to determine the exchange interactions between the A and B sites with exchange constants: [Formula: see text] K (4.1 K), [Formula: see text] K (16.3 K) and [Formula: see text] K (13.8 K) for [Formula: see text]. The temperature dependence of ac susceptibilities [Formula: see text] and [Formula: see text] at different frequencies shows that in bulk samples of [Formula: see text] and [Formula: see text], the transition at T C is the normal second order transition. But for the nanosize [Formula: see text] and 0.2 samples, analysis of the ac susceptibilities shows that the ferrimagnetic transition at T C is followed by a re-entrant spin-glass transition at lower temperatures [Formula: see text] K (138 K) for [Formula: see text] ([Formula: see text]). Analysis of the ac susceptibilities, [Formula: see text] and [Formula: see text], versus T data is done in terms of two scaling laws: (i) Vogel-Fulcher law [Formula: see text] [Formula: see text]; and (ii) power law of critical slowing-down [Formula: see text]. These fits confirm the existence of glassy behavior below T SG with the parameters [Formula: see text] (8.91), [Formula: see text] (9.6 × 10[Formula: see text]) and [Formula: see text] K (∼138 K) for the samples [Formula: see text] (0.2), with similar results obtained for other samples. The linear behavior of the peak maximum in [Formula: see text] versus [Formula: see text] (AT-line) further supports the existence of glassy states in nanosize samples. For [Formula: see text], the temperature and composition dependence of the hysteresis loop parameters are investigated; all the samples with x ⩾ 0.1 have the coercivity H C and remanence [Formula: see text]. Since the results reported here in these nanostructures are significantly different from those in bulk [Formula: see text] [Formula: see text], further investigations of their magnetic structures using neutron diffraction are warranted.

On the nature of magnetic state in the spinel Co2SnO4.

In the spinel Co2SnO4, coexistence of ferrimagnetic ordering below T(N) ≃ 41 K followed by a spin glass state below T(SG) ≃ 39 K was proposed recently based on the temperature dependence of magnetization M(T) data. Here new measurements of the temperature dependence of the specific heat C(P)(T), ac-susceptibilities χ'(T) and χ″(T) measured at frequencies between 0.51 and 1.2 kHz, and the hysteresis loop parameters (coercivity H(C)(T) and remanence M(R)(T)) in two differently prepared samples of Co2SnO4 are reported. The presence of the Co(2+) and Sn(4+) states is confirmed by x-ray photoelectron spectroscopy (XPS) yielding the structure: Co2SnO4 = [Co(2+)][Co(2+)Sn(4+)]O4. The data of C(P) versus T shows only an inflection near 39 K characteristic of spin-glass ordering. The analysis of the frequency dependence of ac-magnetic susceptibility data near 39 K using the Vogel-Fulcher law and the power-law of the critical slowing-down suggests the presence of spin clusters in the system which is close to a spin-glass state. With a decrease in temperature below 39 K, the temperature dependence of the coercivity H(C) and remanence M(R) for the zero-field cooled samples show both H(C) and M(R) reaching their peak magnitudes near 25 K, then decreasing with decreasing T and becoming negligible below 15 K. The plot of C(P)/T versus T also yields a weak inflection near 15 K. This temperature dependence of H(C) and remanence M(R) is likely associated with the different magnitudes of the magnetic moments of Co(2+) ions on the 'A' and 'B' sites and their different temperature dependence.

Magnetic ordering of nickel hydroxide layers 30 Å apart obtained by intercalating dodecyl sulfate.

The nature of magnetic ordering in quasi-2D layered hydroxide of Ni (LH-Ni-DS) with hexagonal structure and synthesized by intercalating dodecyl sulfate (DS) ligand, (C12H25OSO3)(-), between the layers using a hydrothermal technique is investigated. The observation of (00l) peaks up to l = 8 in x-ray diffraction on the sample yields an interlayer spacing c ≃ 30.5 Å and a crystallite size ≃ 16 nm. Assignment of the lines observed in the FTIR spectra to the various groups of the DS ligand confirms the intercalation. From the analysis of detailed investigations of the temperature dependence of the magnetization M at different magnetic fields, ac susceptibilities at frequencies from 0.1 to 1 kHz, and electron magnetic resonance spectra at 9.28 GHz, it is concluded that LH-Ni-DS orders ferromagnetically at TC ≃ 23 K. This TC is about 45% higher than TC ≃ 16 K reported for LH-Ni-Ac with c ≃ 8.6 Å obtained by intercalating an acetate ligand between the layers. The roles of the interlayer dipolar interaction, magnetic anisotropy and exchange interactions in determining TC in LH-Ni-L systems for several ligands L yielding different c-axes are discussed.

The nature of the magnetism in quasi-2D layered α-Ni(OH)2.

The two layered hexagonal hydroxides of Ni are ß-Ni(OH)(2) and α-Ni(OH)(2); ß-Ni(OH)(2) is now known to be an antiferromagnet whereas the nature of the magnetism in α-Ni(OH)(2) is not yet well established. Here, the magnetic properties of α-Ni(OH)(2) with lattice parameters a = 3.02 Å and c = 8.6 Å, and flower-like morphology with petal thickness of approximately equal to 50 Å are reported. Temperature (2-300 K) and magnetic field (up to 65 kOe) dependence of the magnetization and ac susceptibility at f = 0.1-1000 Hz were measured. Analysis of the data yields ferromagnetic ordering in the system with T(C) is approximately equal to 16 K. In addition, a nanosize related blocking temperature T(B) = 8 K and spin-glass-like ordering of the surface spins near 3.5 K are inferred from the ac frequency and dc magnetic field dependence of these transitions. Fitting to the high temperature series and quasi-2D nature of the system is used to determine J(1)/k(B) = 4.38 K (J(2)/k(B) = 0.14 K) for the intraplane (interplane) exchange coupling between the Ni(2+) ions.

Temperature and size dependence of electron magnetic resonance spectra of Ni nanoparticles embedded in an amorphous SiO(2) matrix.

Investigations of spin dynamics in Ni nanoparticles (NPs) with diameters D = 3.8, 11.7, 15 and 21 nm embedded in an amorphous SiO(2) matrix of composition 15/85 (Ni/SiO(2)) are reported using EMR (electron magnetic resonance) spectroscopy at 9.28 GHz. Three resonance lines are observed whose EMR parameters, namely linewidth ΔH, resonance field H(r) and intensity I(o), are measured from 5 to 300 K. Line 1 with temperature-independent ΔH = 50 Oe and g≈2, and intensity varying as 1/T, is shown to result from paramagnetic defects in the SiO(2) matrix. Lines 2 and 3, with g≈2.2 and 8, respectively, and temperature-dependent EMR parameters are assigned to Ni NPs. While line 2 with g≈2.2 is due to the majority of Ni NPs, the source of line 3 is discussed in terms of two possibilities: (i) large clusters of blocked Ni NPs and (ii) the inherent part of the composite asymmetric line made up of lines 2 and 3 predicted by the Raikher-Stepanov (RS) model for dispersed ferromagnets. The temperature dependence of ΔH (full width at half-maximum) of the composite line obtained by integration of the EMR spectra decreases with the increase in temperature, reaching a minimum near 300 K in agreement with the RS model. The observed decreasing asymmetry of the composite absorption spectra with increasing temperature is also in agreement with the predictions of the RS model, thus providing a satisfactory explanation for the observed temperature dependence of the EMR spectra of Ni NPs. Large clusters of blocked Ni NPs as the source of line 3 are ruled out and additional tests for the RS model are proposed. The decreasing magnetization with decreasing particle size of Ni NPs observed here is discussed in terms of the possible roles of the surface disordered spins and Ni-SiO(2) interaction.

Characterization of fine particulate matter produced by combustion of residual fuel oil.

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 microns in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 microns in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM2.5 samples than in the PM2.5+ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO4, while most of the V spectra closely resembled that of vanadyl sulfate (VO.SO4.xH2O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsenate (As+5). X-ray diffraction patterns of the PM2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM2.5 fraction and from 88 to 97% for the PM2.5+ fraction. Based on 13C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.

Surface and bulk infrared modes of crystalline and amorphous silica particles: a study of the relation of surface structure to cytotoxicity of respirable silica.

Surface IR (infrared) modes of crystalline and fumed (amorphous) silica particles, calcined at temperatures up to 1095 degrees C, have been studied by Fourier transform infrared spectroscopy. The ability of these same particles to lyse cells has been measured by a hemolysis protocol. The untreated crystalline and amorphous materials differ by a factor of 40 in specific surface area, and the intensity per unit mass of the sharp surface silanol band near 3745 cm-1 in the amorphous material is an order of magnitude larger than in the crystalline material. A similar difference is observed in the lysing potential of the two materials. The intensity of the silanol band increases after calcination for both materials, reaching peak values near 500 degrees C, followed by a dramatic drop at higher calcination temperatures, and reaching negligible values for materials calcined near 1100 degrees C. The lysing potential data follow essentially the same pattern for both crystalline and fumed silica. These results are consistent with the hypothesis that the surface silanol groups are involved in cell lysis. Further experiments are suggested to evaluate the relationship between the surface structure of silica particles and their potential cytotoxicity.

Chemiluminescence of guinea pig peritoneal macrophages stimulated by immune precipitates and soluble immune complexes.

The chemiluminescence (CL) response of guinea pig peritoneal macrophages to immune precipitates and soluble immune complexes has been investigated. The rapid burst of intense light emission observed in response to both stimuli, was inhibited by superoxide dismutase (SOD). With soluble immune complexes, this was followed by prolonged CL of lower intensity susceptible to both SOD and catalase inhibition. The magnitude of the CL response was directly related to seize the size of the soluble complexes reacting with the macrophages. These findings suggest that circulating, as distinct from deposited immune complexes, may play a role in the pathogenesis of complex-mediated diseases.