(121,123)Sb and (75)As NMR and NQR investigation of the tetrahedrite (Cu12Sb4S13)--Tennantite (Cu12As4S13) system and other metal arsenides.

This work is motivated by the recent developments in online minerals analysis in the mining and minerals processing industry via nuclear quadrupole resonance (NQR). Here we describe a nuclear magnetic resonance (NMR) and NQR study of the minerals tennantite (Cu12As4S13) and tetrahedrite (Cu12 Sb4S13). In the first part NQR lines associated with (75)As in tennantite and (121,123)Sb isotopes in tetrahedrite are reported. The spectroscopy has been restricted to an ambient temperature studies in accord with typical industrial conditions. The second part of this contribution reports nuclear quadrupole-perturbed NMR findings on further, only partially characterised, metal arsenides. The findings enhance the detection capabilities of NQR based analysers for online measurement applications and may aid to control arsenic and antimony concentrations in metal processing stages.

(75)As NQR studies on FeAs2.

(75)As NQR spectra and relaxation times of synthetic and natural FeAs2 samples have been studied at variable static magnetic field and temperature. FeAs2 is a well understood diamagnetic semiconductor and occurs as the natural mineral lollingite in selected ore deposits. We observed a spin-spin relaxation time enhancement of up to five in synthetic powders in the presence of a weak external static magnetic field. The effect is of interest with regard to signal-to-noise ratio improvement for materials characterization applications where broad NQR absorption lines are excited with wideband pulse sequences.

75As, 63Cu NMR and NQR characterization of selected arsenic minerals.

The direct measurement and identification of solid state arsenic phases using (75)As NMR is made difficult by the simultaneous conditions of large quadrupole moment and low coordination symmetry in many compounds. However, specific arsenic minerals can efficiently be detected and discriminated via nuclear quadrupolar resonance (NQR). We report on the first NMR and NQR measurements in the natural minerals enargite (Cu3AsS4), niccolite (NiAs), arsenopyrite (FeAsS) and loellingite (FeAs2). The NQR frequencies have been determined from both high-field NMR powder patterns and via zero-field frequency sweeps. Density functional theory (DFT) based ab initio calculations support the experimental results. The compounds studied here are common in terms of the known set of As-containing minerals. They are sometimes encountered in the context of base metal or gold mining. The study represents a significant addition to the list of arsenic minerals that can now be detected with NQR techniques.

Pseudomorphic 2A--> 2M--> 2H phase transitions in lanthanum strontium germanate electrolyte apatites.

Apatite-like materials are of considerable interest as potential solid oxide fuel cell electrolytes, although their structural vagaries continue to attract significant discussion. Understanding these features is crucial both to explain the oxide ion conduction process and to optimise it. As the composition of putative P6(3)/m apatites with ideal formula [A(I)(4)][A(II)(6)][(BO(4))(6)][X](2) is varied the [A(I)(4)(BO(4))(6)] framework will flex to better accommodate the [A(II)(6)X(2)] tunnel component through adjustment of the A(I)O(6) metaprism twist angle (varphi). The space group theory prescribes that framework adaptation during phase changes must lead to one of the maximal non-isomorphic subgroups of P6(3)/m (P2(1), P2(1)/m, P1[combining macron]). These adaptations correlate with oxygen ion conduction, and become crucial especially when the tunnels are filled by relatively small ions and/or partially occupied, and if interstitial oxygens are located in the framework. Detecting and completely describing these lower symmetry structures can be challenging, as it is difficult to precisely control apatite stoichiometry and small departures from the hexagonal metric may be near the limits of detection. Using a combination of diffraction and spectroscopic techniques it is shown that lanthanum strontium germanate oxide electrolytes crystallise as triclinic (A), monoclinic (M) and hexagonal (H) bi-layer pseudomorphs with the composition ranges: [La(10-x)Sr(x)][(GeO(4))(5+x/2)(GeO(5))(1-x/2)][O(2)] (0

25Mg NMR site analysis in metals and intermetallics.

Nuclear magnetic resonance (NMR) of the low abundance and low gyromagnetic ratio isotope (25)Mg, I=5/2, 2.606MHz/T, 10% abundant, is shown here to provide an informative probe for phase identification, site symmetry and site multiplicity of the intermetallic compounds which occur as strengthening precipitate phases in lightweight alloys. The intermetallics discussed here, Mg(17)Al(12), MgZn(2), Mg(2)Al(3) and Al(2)CuMg, are the final equilibrium precipitate phases in a number of Mg- and Al-based heat-treatable alloys. The (25)Mg spectra of Mg in Al-10at%Mg alloy show the progressive precipitation of Mg(2)Al(3) from Mg in solid solution as a function of annealing time at 150 degrees C. Also reported are (25)Mg spectra for CuMg(2), Mg(44)Al(15)Zn(41) and Mg(2)Sn, along with the counter atom (67)Zn and (63)Cu NMR spectra for MgZn(2) and CuMg(2). All spectra are simulated to determine nuclear interaction parameters and confirm site occupancy.

NMR analysis of ferromagnets: Fe oxides.

A short historical review is given on internal field NMR of ferromagnets, illustrated with recent pulsed NMR spectra of the elemental ferromagnets Fe, Co and Ni and the Fe-oxides magnetite, maghemite and hematite, which, with the exception of maghemite, have resonance frequencies first reported over 45 years ago. Since the magnetic hyperfine field at the nucleus is not known a priori, the original search frequency motivations are discussed along with the mechanisms for the initially much larger than expected ( approximately 10(3)) NMR signals that were observed. The (57)Fe spectra of the three principal Fe-oxide ferromagnets, magnetite (Fe(3)O(4)), maghemite (gamma-Fe(2)O(3)) and hematite (alpha-Fe(2)O(3)), obtained here under uniform spectroscopic conditions, are then discussed in more detail, with a focus on the influence of particle size and vacancy content on the hyperfine fields.

The crystal chemistry of ferric oxyhydroxyapatite.

Ferric hydroxyapatites (Fe-HAp) and oxyapatites (Fe-OAp) of nominal composition [Ca(10-x)Fe(x)(3+)][(PO(4))(6)][(OH)(2-x)O(x)] (0 < or = x < or = 0.5) were synthesized from a coprecipitated precursor calcined under flowing nitrogen. The solid solubility of iron was temperature-dependent, varying from x = 0.5 after firing at 600 degrees C to x approximately 0.2 at 1000 degrees C, beyond which Fe-OAp was progressively replaced by tricalcium phosphate (Fe-TCP). Crystal size (13-116 nm) was controlled by iron content and calcination temperature. Ferric iron replaces calcium by two altervalent mechanisms in which carbonate and oxygen are incorporated as counterions. At low iron loadings, carbonate predominantly displaces hydroxyl in the apatite channels (Ca(2+) + OH(-) --> Fe(3+) + CO(3)(2-)), while at higher loadings, "interstitial" oxygen is tenanted in the framework (2Ca(2+) + (vac) --> 2Fe(3+) + O(2+)). Although Fe(3+) is smaller than Ca(2+), the unit cell dilates as iron enters apatite, providing evidence of oxygen injection that converts PO(4) tetrahedra to PO(5) trigonal bipyramids, leading to the crystal chemical formula [Ca(10-x)Fe(x)][(PO(4))(6-x/2)(PO(5))(x/2)][(OH)(2-y)O(2y)] (x < or = 0.5). A discontinuity in unit cell expansion at x approximately 0.2 combined with a substantial reduction of the carbonate FTIR fingerprint shows that oxygen infusion, rather than tunnel hydroxyl displacement, is dominant beyond this loading. This behavior is in contrast to ferrous-fluorapatite where Ca(2+) --> Fe(2+) aliovalent replacement does not require oxygen penetration and the cell volume contracts with iron loading. All of the materials were paramagnetic, but at low iron concentrations, a transition arising from crystallographic modification or a change in spin ordering is observed at 90 K. The excipient behavior of Fe-OAp was superior to that of HAp and may be linked to the crystalline component or mediated by a ubiquitous nondiffracting amorphous phase. Fe-HAp and Fe-OAp are not intrinsically suitable magnetic agents for drug delivery but may be useful in reactive cements that promote osteoblast proliferation.

Solid-state NMR characterisation of the thermal transformation of a Hungarian white illite.

(1)H, (27)Al, (29)Si and (39)K solid-state NMR are reported from a Hungarian illite 2:1 clay for samples heated up 1600 degrees C. This single-phase sample has a small amount of aluminium substitution in the silica layer and very low iron-content ( approximately 0.4wt%). Thermal analysis shows several events that can be related to features in the NMR spectra, and hence changes in the atomic scale structure. As dehydroxylation occurs there is increasing AlO(4) and AlO(5)-contents. The silica and gibbsite layers become increasingly separated as the dehydroxylation progresses. Between 900 and 1000 degrees C the silica layer forms a potassium aluminosilicate glass. The gibbsite-layer forms spinel/gamma-Al(2)O(3) and some aluminium-rich mullite. Then on heating to 1600 degrees C changes in the (29)Si and (27)Al MAS NMR spectra are consistent with the aluminosilicate glass increasing its aluminium-content, the amount of mullite increasing probably with its silicon-content also increasing, and some alpha-Al(2)O(3) forming.

95Mo NMR: hyperfine interactions in MoO3, MoS2, MoSe2 Mo3Se4, MoSi2 and Mo2C.

Nuclear hyperfine interactions have been obtained by nuclear magnetic resonance (NMR) for 95Mo in a number of binary Mo compounds, both insulators and metals, which illustrate the interplay between nuclear quadrupole and chemical (Knight) shift terms. The insulating phases are characterised by nuclear spin lattice relaxation times greater than 100 s, demonstrating the ineffectiveness of indirect phonon Raman relaxation for these compounds.

47,49Ti NMR: hyperfine interactions in oxides and metals.

A 47,49Ti NMR characterisation is given of various polymorphs of TiO2 (anatase, rutile and brookite), Ti2O3, perovskites CaTiO3 and BaTiO3, FeTiO3, TiB2, titanium metal, the titanium aluminides Ti3Al, TiAl, TiAl2, TiAl3, and TiAg. Values of chemical or Knight shift, nuclear quadrupole coupling constant and asymmetry parameter were derived from the (1/2, -1/2) powder lineshapes. For TiB2, titanium metal, TiAl, and TiAl3, where +/- (1/2, 3/2), and higher satellite transitions were observed, a value for the axial component of the Knight shift was obtained.

14N NMR in AlN and BN.

A characterisation by 14N NMR of the binary nitrides AlN and BN is presented. Both the static and magic angle spinning (MAS) lineshapes have been investigated in order to determine, or set upper limits on, the nuclear quadrupole coupling (Cq) at the nitrogen site. Additional data are given for the Cq values at the Al and B sites. A comparison is made with other similar (mainly wurtzite) binary compounds for which Cq is known at each atomic site.

Electric quadrupole interaction of 137Ba in barium fluorohalides.

The X-ray storage phosphor materials BaFC1 and BaFBr differ greatly in their 137Ba nuclear electric quadrupole interaction, despite a common crystal structure. The quadrupole coupling constant in BaFCl is relatively small and increases rapidly with temperature, in an unusual manner: [CQ[ = 1.7 MHz at T = 296 K, CQ-1(delta CQ/delta T)p = 1.7 x 10(-3) K-1. The coupling BaFBr is [CQ[ = 17.0 MHz at 296 K. The difference in quadrupole coupling at room temperature is explained using an electrostatic point-charge model of the crystals.

Solid state NMR characterisation of crystalline Na2O-ZrO2-SiO2 phases.

The NMR interactions of crystalline phases in the system Na2O-ZrO2-SiO2 have been studied by a combination of static and magic angle spinning NMR methods for the first time. A full multinuclear (17O, 23Na, 29Si and 91Zr) approach has been employed that allows the phases to be clearly identified. NMR interactions such as 29Si isotropic chemical shift correlate with the known structural units present. For 23Na the the different sites can often be distinguished on the basis of differing quadrupolar interactions.

Structural characterisation of Na2ZrO3.

A combination of X-ray and electron diffraction, electron microscopy and solid-state nuclear magnetic resonance (NMR) has been used to elucidate the structure and the ordering of Na2ZrO3. The diffraction data confirm a monoclinic crystal structure. A sample prepared by a conventional solid-state reaction of the components is shown by both X-ray diffraction and electron microscope imaging to have an extremely high concentration of planar defects associated with stacking disorder of the planes along the c-axis. The incidence of these defects is significantly reduced in a sample recrystallised from a bismuth oxide flux. NMR indicates that the local coordinations are well defined in both samples but with some sharpening of the spectra from the recrystallised sample indicative of the increase of long-range order. The 23Na magic angle spinning (MAS) NMR spectra clearly show three distinct sites with widely differing quadrupolar interaction parameters that can be related to the known site symmetries. Two distinct oxygen resonances are observed in the MAS NMR spectrum from an 17O-enriched sample while the static 91Zr NMR spectrum can be simulated with one set of interaction parameters.

139La nuclear magnetic resonance characterisation of La2O3 and La1-xSrxMO3 where M = Cr, Mn or Co.

139La Nuclear magnetic resonance (NMR) spectra have been used to obtain nuclear quadrupole coupling parameters for La2O3 and a series of perovskites La1-xSrxMO3 (where M = Cr, Mn or Co). Depending on the doping level of SrO2 these materials are either paramagnetic or ferromagnetic at room temperature. Magnetic transferred hyperfine effects are strongly in evidence in the Mn compounds. A 59Co NMR spectrum was observed in LaCoO3. A precision measurement of the nuclear quadrupole coupling constant in La2O3 was made by nuclear quadrupole resonance (NQR) spectroscopy.

91Zr NMR characterisation of phases in transformation toughened zirconia.

A detailed 91Zr NMR investigation is presented of the five component (cubic, monoclinic, tetragonal, orthorhombic and delta) phase mixture in the transformation toughened engineering ceramic, magnesia-partially-stabilised zirconia (MgPSZ). The phases are distinguished on the basis of the quadrupole interaction displayed in the powder pattern of the 91Zr(1/2, -1/2) transition. This paper reports: (i) the first characterisation of the magnesia-fully-stabilised cubic phase at the eutectic composition (13.5 mol% MgO); (ii) the observation of a poorly ordered tetragonal phase on fast cooling ZrO2 (9.3 mol% MgO) from the cubic phase field at 1720 degrees C, and the subsequent growth and ordering of the tetragonal phase precipitates due to further annealing; (iii) the observation of the (partial) transformation of the cubic phase to the ordered delta-phase (Mg2Zr5O12) on annealing MgPSZ at 1100 degrees C for 8 h; and (iv) the observation of the transformation of the tetragonal phase into the orthorhombic phase after cooling in liquid nitrogen, and the reverse transformation after heating to 600 degrees C.