Exchange reactions of Na-montmorillonite with zirconyl chloride solutions give products with basal spacings near 18 Å which are stable to 500°C and have surface areas of the order of 300–400 m2/g. The Na ions are exchanged with tetrameric hydroxy cations [Zr4(OH)14•nH2O]2+. The high surface area is attributed to the porosity formed by stable zirconium oxide “pillars” formed by dehydroxylation of the complex cation. The nitrogen adsorption isotherms are of Langmuir type and are consistent with adsorption in interlayer micropores. Reduced-charge montmorillonites, formed by application of the Hofmann-Klemen procedure, give either similar or slightly smaller surface areas.

Electron probe microanalysis (EPMA) is based on physical relations between measured X-ray intensities of characteristic lines and their X-ray production efficiency, which depends on the specimen composition. The quality of the analysis results relies on how realistically the physical relations describe the generation and emission of X-rays. Special experiments are necessary to measure X-ray production efficiencies. A challenge in these experiments is the determination of the detection efficiency of the spectrometer as a function of the photon energy. An energy-dispersive spectrometer was used in this work, for which the efficiency was determined at metrological synchrotron beamlines with an accuracy of ±2%. X-ray production efficiencies for the L series and the Kα series of copper and zirconium and for the M and L series of tungsten were determined at energies up to 30 keV in a scanning electron microscope. These experimental values were compared with calculated X-ray production efficiencies using physical relations and material constants applied in EPMA. The objective of the comparison is the further improvement of EPMA algorithms as well as extending the available database for X-ray production efficiencies. Experimental data for the X-ray production efficiency are also useful for the assessment of spectrum simulation software.

The effect of laser fluence and nature of ambient environments on the sputtering yield, surface modifications, crater depth, UV-visible absorption spectra, chemical composition, and micro hardness of Zr has been investigated. Nd: YAG laser (532 nm, 10 Hz, 6 ns) at different fluences varying from 16 to 60.8 Jcm−2 was employed as an irradiation source. All measurements are performed under two ambient environments of Ar and O2 at a constant pressure of 10 Torr. Quartz crystal microbalance has been employed for the measurement of sputtering yield of laser irradiated Zr. It is revealed that sputtering yield increases monotonically with increasing fluence under both environments however, it is higher in Ar as compared to O2 environment. Scanning electron microscope (SEM) has been used to explore the surface morphology. SEM analysis exhibits the formation of cones, ridges, and cracks at the central ablated areas whereas, laser-induced periodic surface structures, periodic ridges and sharp cones are observed at inner boundaries in both environments of Ar and O2. Sharp spikes are observed in both environments, however, their height and distinctness are more pronounced in Ar as compared to O2. Cones are characteristic features in Ar, whereas, cavities and channels are dominant features in O2 environment at outer boundaries. The formation and growth of surface structures are dependent upon laser fluence and ambient gas nature. The depth profilometry has been used to measure the crater depth of irradiated Zr target by using an optical microscope. UV visible spectroscopy and energy-dispersive X-ray analyses reveal the oxide formation in the case of Zr irradiation in O2 environment. The Vicker Micro-hardness tester has been employed to measure the hardness. The higher observed values of sputtering yield, crater depth and hardness of laser ablated Zr in Ar as compared to O2 are well correlated with distinct surface structures.

Ilmenites from alkaline basic dykes in the Gardar province, south Greenland have Zr contents up to 3850ppm and Nb contents up to 1030ppm. These elements substitute for Ti in the octahedral site. These are amongst the highest recorded Zr and Nb contents for ilmenites, giving distribution coefficients (Kdilmenite/matrix) for Zr up to 11.6 and Nb up to 70.3. Fractionation of ilmenite may thus have a dramatic effect on residual Zr and Nb contents. These effects are discussed in relation to the use of trace element tectonomagmatic discrimination diagrams.

The Cnoc Rhaonastil minor dolerite intrusion on Islay, NW Scotland represents a single body of alkali olivine basalt magma which differentiated in situ, from leucodolerite, through teschenite to minor nepheline syenite. The syenites occur as isolated nests and pegmatitic schlieren within the leucodolerite, and schlieren of gabbroic pegmatite also occur at the margin of the teschenite. The differentiated rocks contain pyroxene, amphibole and biotite of variable compositions which reflect both primary fractionation processes and late-stage deuteric alteration and reaction.Mafic phases within the gabbroic pegmatite, teschenite and syenite are typically rimmed and speckled with biotite, the composition of which is controlled by the local environment of crystallization. The nepheline syenites contain primary ferro-kaersutite which, where in contact with interstitial patches, has been altered to arfvedsonite, which occasionally contains up to 1.2 wt.% ZrO2. The occurrence of Zr-arfvedsonite (and of Zr-aegirine) in interstitial patches suggests that variably trace element-enriched domains existed within the residual melts on very small scales.

Samples of artificially aged Nirex reference vault backfill (NRVB) were prepared by progressive leaching with deionized water, after which some of the samples underwent hydrothermal treatment. Compared to unaltered NRVB, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) provided evidence for the ageing resulting in alteration of the mineralogy, in particular the absence of portlandite was observed. The specific surface area of NRVB initially increased due to leaching, but then decreased after further leaching.

Sorption distribution ratios (R D values) of uranium(VI), neptunium(IV), tin and zirconium onto aged NRVB samples were measured using the batch sorption technique. For all four elements, there was little difference between R D values for aged NRVB and those for untreated material. The most probable explanation for these findings is that even though the ageing treatments altered the NRVB mineralogy, calcium silicate hydrate (C-S-H) phases are responsible for most of the radionuclide uptake and their transformation to more crystalline forms has little effect on the bulk sorption capacity of the aged material.

Zirconium and Hf are nearly identical geochemically, and therefore most of the crust maintains near-chondritic Zr/Hf ratios of ∼35–40. By contrast, many high-silica rhyolites and granites have anomalously low Zr/Hf (15–30). As zircon is the primary reservoir for both Zr and Hf and preferentially incorporates Zr, crystallization of zircon controls Zr/Hf, imprinting low Zr/Hf on coexisting melt. Thus, low Zr/Hf is a unique fingerprint of effective magmatic fractionation in the crust. Age and compositional zonation in zircons themselves provide a record of the thermal and compositional histories of magmatic systems. High Hf (low Zr/Hf) in zircon zones demonstrates growth from fractionated melt, and Ti provides an estimate of temperature of crystallization (TTiZ) (Watson and Harrison, 2005). Whole-rock Zr/Hf and zircon zonation in the Spirit Mountain batholith, Nevada, document repeated fractionation and thermal fluctuations. Ratios of Zr/Hf are ∼307–40 for cumulates and 18–30 for high-SiO2 granites. In zircons, Hf (and U) are inversely correlated with Ti, and concentrations indicate large fluctuations in melt composition and TTiZ (>100°C) for individual zircons. Such variations are consistent with field relations and ion-probe zircon geochronology that indicate a >1 million year history of repeated replenishment, fractionation, and extraction of melt from crystal mush to form the low Zr/Hf high-SiO2 zone.

This paper reports the first in-situ finding of perrierite-(Ce) in Latium. The mineral occurs as brownish-red, transparent, well-developed, euhedral, prismatic crystals inside the miarolitic cavities of a holocrystalline ejectum from La Mola, Monti dell'Anguillara district, Sabatini volcanic complex.

The cell parameters (from Gandolfi film) are (in Å): a = 13.629(9), b = 5.727(1), c = 11.715(6), β(°) = 113.74(2), V(Å3) = 835.5(9). The crystal-chemical formula, based on microprobe analysis of one grain, is:

This perrierite is the most Zr-rich described so far. The entry of Zr in the C site of the structure is related to the substitution of large amounts of Ca in the A site, according to the charge balancing relationship:

The genesis of perrierite-(Ce) from La Mola is linked to late pneumatolitic-pegmatitic hypabyssal stages of the regional volcanic activity.

Th- and Zr-bearing perovskite and Zr-rich Ti garnet are described from the Polino calcite carbonatite, Italy. The garnets contain 6.05-7.50 wt.% ZrO2 in cores and up to 15.80 wt.% in rims. Silicon is low in these garnets and substantial Al and Fe 3+ has been assigned to the tetrahedral sites. A strong correlation of Si with Zr from published data suggests the possibility that some Zr may also be tetrahedrally coordinated. However, the chemistry alone does not constrain the site distribution of Fe, Ti, Zr and Mg unambiguously. The perovskites are very unusual in containing 2.81-3.27 wt.% ZrO2 and 1.48-1.71 wt.% ThO2. For comparison, new analyses are presented of the zirconium garnet kimzeyite and coexisting perovskite from the type locality at Magnet Cove.

Soda-rich pyroxenes in felsic rocks from the Warrumbungle Volcano, central New South Wales, contain up to 14.5 wt. % ZrO2, which is more than double the previously reported maximum ZrO2 in pyroxene. Zr is believed to enter aegirine as the component Na(Fe2+,Mn,Mg)0.5Zr0.5Si2O6 via the coupled substitution: (Fe2+,Mn,Mg)VI+ZrVI = 2(Fe3+)VI. This component exceeds 50 mol. % in some analyses.

Pronounced pyroxene Zr-enrichment is restricted to rocks in which sodic amphibole is the major ferromagnesian mineral, with pyroxene only a minor late-stage phase. The Zr-rich pyroxenes resulted from a combination of host lava peralkalinity, low oxygen fugacity, rapid disequilibrium crystallization and low mobility of the Zr ion. These factors collectively led to the development of interstitial Zr-enriched microdomains in the felsic hosts during their final stages of crystallization.

The construction of zirconium (Zr) budgets for metamorphic reactions in high-grade rocks provides new insight into zircon growth during metamorphism. In this study we target reactions involving garnet, as they enable zircon growth to be related to known pressure and temperature conditions. Two reactions involving the breakdown of Zr-bearing garnet from Rogaland, SW Norway have been investigated in detail, showing contrasting behaviour of Zr, with zircon formation being subject to the solubility of Zr in product phases. In the decompression reaction garnet + sillimanite + quartz → cordierite, Zr released during garnet breakdown cannot be incorporated into the cordierite structure, resulting in zircon nucleation and growth. In contrast, for the reaction garnet + biotite + sillimanite + quartz → osumilite + orthopyroxene + spinel + magnetite, no new zircon growth takes place, despite the garnet involved containing more than double the Zr concentration of the former reaction. In the latter case, all the Zr released by garnet breakdown can be detected in the product phases osumilite and orthopyroxene, thereby preventing growth of new metamorphic zircon. This study highlights the potential for high resolution geochronology in metamorphic rocks by relating zircon growth to specific metamorphic reactions.

Rutile grains occur extensively in host phases of biotite and quartz-feldspar aggregate in high-temperature paragneisses of the Mogok metamorphic belt of Myanmar. They occur as an isolated phase and sometimes show intergrowth texture with ilmenite. Most rutile grains contain up to 3.7 wt.% Nb2O5, which shows positive correlations with Fe and trivalent elements. Niobium substitutes for Ti by a coupled substitution with the trivalent cations (M3+) of Nb5+M3+Ti4+-2. Fine-grained rutile grains included in ilmenite are distinctly poor in Nb (<0.1 wt.% as Nb2O5) and contain Fe of 1.7–3.2 wt.% as Fe2O3, suggesting vacancybearing substitution of Fe3+4 Ti4+-3□–1, where □ indicates a vacancy. The rutile grains in the felsic phases contain high Zr contents of up to 4200 ppm, suggesting equilibrium temperatures over 800°C using the Ti-in-rutile geothermometer. These high-temperature conditions are consistent with those estimated by conventional methods reported in the literature and suggest widespread occurrences of the upperamphibolite and granulite facies metamorphic rocks in the middle segment of the Mogok metamorphic belt. In contrast, the Zr contents of rutile grains in biotite are usually <1000 ppm, implying equilibrium temperatures lower than 750°C. Most of the rutile grains poorer in Zr might have been included in biotite and were isolated from the zircon-bearing system during an early stage of prograde metamorphism. Some other rutile grains poorer in Zr might have been an exsolved phase from Ti-rich biotite during retrograde metamorphism, which was furthered by the infiltration of metamorphic fluid under lower-amphibolite facies conditions.

Two series of zirconium samples were investigated by neutron and X-ray diffraction. First series of the samples was deformed at room temperature (RT), whereas the second series was deformed at 300 °C. Both series were deformed on uniaxial tensile machine INSTRON 5882 from strain 0 to 30% (strain step was 5%). The neutronographic texture measurements were performed on the KSN-2 neutron diffractometer located at the research reactor LVR-15 in the Nuclear Research Institute, plc. Rez, Czech Republic. The X-ray measurements were performed at the theta/theta X'Pert PRO diffractometer with the Cr X-ray tube. Observed data were processed by the software packages GSAS and X'Pert Texture. Preferential orientation of the $\left({10\bar 10} \right)$ and $\left({11\bar 20} \right)$ plane poles is found to be parallel to the rolling direction for both tested deformation series. Poles of the $\lpar 10\bar 12\rpar $ and $\lpar 10\bar 13\rpar $ planes tend to be parallel to the normal direction (Tables II and III). Orientation of the basal poles is tilted by 45° from the normal direction toward the transverse direction. Sharpness of the resulting texture increases with extends of the applied deformation as well as with rise of the tensile test temperature from the RT level to 300 °C.

In situ deformation studies of polycrystalline materials using diffraction are an established method to understand elastic and plastic deformation of materials. Studies of active deformation mechanisms, the interplay of deformation with texture, and ultimately the development of predictive capabilities for deformation modeling are an active field of research. Parameters studied by diffraction are typically lattice strains and texture evolution, which coupled with the macroscopic flow curve allow for improved understanding of the micro-mechanics of deformation. We performed a study of the uniaxial deformation of Zircaloy-2 at 2 GPa at the 13-BM-D beamline at the Advanced Photon Source. The deformation-DIA apparatus generates a confining hydrostatic pressure using a cubic anvil setup. Two differential rams allow an increase (compressive load) or decrease (tensile load) of the uniaxial straining in the vertical direction, allowing studies of plastic deformation at high pressures. In this paper, we describe how macroscopic strains, hydrostatic pressure, and uniaxial strains are derived and present some brief results.

A single-pulse X-ray diffraction (XRD) diagnostic has been developed for the investigation of shocked material properties on a very short time scale. The diagnostic, which consists of a 37-stage Marx bank high-voltage pulse generator coupled to a needle-and-washer electron beam diode via coaxial cable, produces line-and-bremsstrahlung X-ray emission in a 40 ns pulse. The molybdenum anode produces 0.71 Å characteristic Kα lines used for diffraction. The X-ray beam passes through a pinhole collimator and is incident on the sample with an approximately 2 mm×5 mm spot and 1° full width at half maximum angular divergence. Coherent scattering from the sample produces a Debye-Scherrer diffraction pattern on an image plate located at 75 mm from the polycrystalline sample surface. An experimental study of the polycrystalline structures of zirconium and tin under high-pressure shock loading has been conducted with single-pulse XRD. The experimental targets were 0.1-mm-thick foils of zirconium and tin using 0.4-mm-thick vitreous carbon back windows for shock loading, and the shocks were produced by either Detasheet or PBX-9501 high explosives buffered by 1-mm-thick 6061-T6 aluminum. The diffraction patterns from both shocked zirconium and tin indicated a phase transition into a polymorphic mix of amorphous and new solid phases.

Development of metallic glasses is hindered by the difficulties in manufacturing bulk parts. We report on the preparation of glassy alloys using the spark plasma sintering of gas atomized powders. The Zr57Cu20Al10Ni8Ti5 alloy processed has a high glass forming ability. Densification is obtained at the glass transition temperature (390 °C) under high pressure (≈500 MPa). Systematic study of the effect of powder particles size and sintering time is performed through structural and thermal analyses. Local and partial devitrification of the amorphous alloy is detected, resulting from local temperature overshoots. From these analyses, an approach of the spark plasma sintering mechanism of metallic glasses is proposed.