Crystalline Quartz Research Articles

Mining Wastes of an Albite Deposit as Raw Materials for Vitrified Mullite Ceramics

In this work, an examination of mining wastes of an albite deposit in south Spain was carried out using X-ray Fluorescence (XRF), X-ray diffraction (XRD), particle size analysis, thermo-dilatometry and Differential Thermal Analysis (DTA) and Thermogravimetric (TG) analysis, followed by the determination of the main ceramic properties. The albite content in two selected samples was high (65–40 wt. %), accompanied by quartz (25–40 wt. %) and other minor minerals identified by XRD, mainly kaolinite, in agreement with the high content of silica and alumina determined by XRF. The content of Na2O was in the range 5.44–3.09 wt. %, being associated with albite. The iron content was very low (<0.75 wt. %). The kaolinite content in the waste was estimated from ~8 to 32 wt. %. The particle size analysis indicated values of 11–31 wt. % of particles <63 µm. The ceramic properties of fired samples (1000–1350 °C) showed progressive shrinkage by the thermal effect, with water absorption and open porosity almost at zero at 1200–1250 °C. At 1200 °C, the bulk density reached a maximum value of 2.38 g/cm3. An abrupt change in the phase evolution by XRD was found from 1150 to 1200 °C, with the disappearance of albite by melting in accordance with the predictions of the phase diagram SiO2-Al2O3-Na2O and the system albite-quartz. These fired materials contained as main crystalline phases quartz and mullite. Quartz was present in the raw samples and mullite was formed by decomposition of kaolinite. The observation of mullite forming needle-shape crystals was revealed by Scanning Electron Microscopy (SEM). The formation of fully densified and vitrified mullite materials by firing treatments was demonstrated.

High-sensitive absorption measurement in ultrapure quartz glasses and crystals using time-resolved photothermal common-pass interferometry and its possible prospects

We describe the functional capabilities of the time-resolved photothermal common-pass interferometry method. For two thermo-optical effect-based methods, photothermal common-pass interferometry and time-resolved photothermal common-pass interferometry, the achieved detection limit for absorption measurements in ultrapure quartz glasses (5 × 10−7 cm−1 and 2 × 10−9 cm−1, respectively) is given. The problem of calculating the variation of the refractive index tensor under local heating trigonal-symmetric crystals of class 32 by a focused laser beam is considered. For these crystals, it is shown that the problem of the influence of deformations on the measured signal is reduced to determine a thermo-optical parameter (an analog of dn/dT). The calculation of this parameter does not require a complete solution to the strain problem when the crystals are heated locally by laser radiation. The formulas for calculating the thermo-optical parameter P and its numerical values are presented. They are required to calibrate absorption measurements in crystalline quartz using the time-resolved photothermal common-pass interferometry scheme. For a full understanding, formulas of the theory of equilibrium deformations used in this study are presented. An analysis of the relevance of improving the thermo-optical method sensitivity for concentration measurements of pollutant inclusions in crystals, ultrapure quartz glasses, and ambient air is presented.

Microbial signatures from speleothems: A petrographic and scanning electron microscopy study of coralloids from the Koněprusy Caves (the Bohemian Karst, Czech Republic)

AbstractExotic carbonate – siliceous coralloid speleothems of the Koněprusy Caves, which consist of dominant aggregates of feather‐like, radial fibrous, dogtooth and gothic‐arch calcite crystals, contain a diversity of petrified fossil microbes entombed in siliceous parts of the speleothems. Although a complete diagenetic continuum of SiO2 polymorphs, ranging from opal‐A, through opal‐CT, to moganite and crystalline quartz, was identified to form thin irregular laminae and the infills of secondary pores throughout the speleothems, the microbes have been preserved only in opal aggregates concentrated in younger growth zones of the speleothems. The identified biomorphic bodies included ovoid and spheroidal forms, interpreted as coccoid microbes, and tubular, bent and elongated forms believed to represent putative silicified filamentous microbes of unknown taxonomic affinity. Other biomorphic microstructures resembling biofilms, and plastic deformations and binary fissions of individual coccoid microbes have also been recognized. The silicified microbes, most of which have been heavily encrusted in situ, still reveal the presence of organic carbon and other biogenic elements detectable beneath their opal coats. Micro‐cavities beneath and around coccoid microbes, interpreted as micro‐borings, suggest that the microbes were able to remove the opal substrate by chemical etching. The morphology and mineralization styles of the microbes, the age of which was estimated to be in the range of 100 to 102 ka, exhibit similarities to silicified microbes from present‐day siliceous hot‐spring geysers and travertines. In contrast to the siliceous parts of the coralloids, the calcite crystals forming the matrix of the speleothems do not contain any calcified microfossils. However, deeply etched calcite crystals, spiky calcite sub‐crystals, needle‐fibre calcite and sparmicrite grains indicate that the processes of calcite dissolution–precipitation mediated by the microbes may have also affected the speleothem exteriors.

Výrazně zonální tetraedrit-tennantit z Kramolína, rudní revír Michalovy Hory (Česká republika)

The crystals of significantly zonal tetrahedrite-tennantite were found in the mine dump material of the Grubenwall 42 mine, Kramolín, the Michalovy Hory ore district, western Bohemia (Czech Republic). Tetrahedrite-tennantite forms layer of tetrahedral, partly corroded crystals up to 1 mm in size on a crust of crystalline quartz in association with chalcopyrite and cerussite. Individual zones in oscillatory zoned crystals are represented by three members of tetrahedrite group minerals - tetrahedrite-(Zn), tennantite-(Zn) and rare tennantite-(Fe). The observed range of AsSb-1 substitution is unusual within a single crystal and indicates high variability of the As/Sb ratio in the hydrothermal fluids.

Diatomite – evaluation of physico-mechanical, chemical, mineralogical and thermal properties

Diatomite is one of the most intensively examined raw materials in the materials industry with a broad range of various applications. The diatomite sample, collected from Vitačevo plateau in the vicinity of Kavadarci, was fully characterized by means of physical-mechanical, chemical, XRPD, SEM, TEM, DTA/TGA and IR techniques. The physical-mechanical features pointed out to soft, light, white to gray rock with shell-like structure exhibiting compressive strength from 4.65–4.88 MPa in dry form, whereas the total porosity ranges 70–72% and the density is 2.06–2.09 g/cm3. The chemical analysis of the diatomite revealed that SiO2 content exceeds 91%. The results from the X-ray powder diffraction indicate predominant amorphous SiO2 phase associated with minor presence of crystalline quartz, muscovite, chlorites and plagioclase. The IR spectrum of the diatomite manifested characteristic bands for amorphous silica at 799 cm–1 and 1101 cm–1. DTA/TGA results display great thermal stability of the sample remaining amorphous up to 1050ºC whereas the SEM analysis determined the morphology, surface characteristics and the nanometric pores in the raw material. Thus, the studied diatomite is classified as a natural nanomaterial that is suitable for broad application in various construction materials, refractory ceramics, special oxide ceramics, and also finds potential use in filtering, adsorbent, catalysts, food and pharmaceutical industries.

Псевдоморфообразование по раковинам силурийских брахиопод

The analysis of paleontological data, the study of mineral matter transformation involving live organisms in various rocks is important for the understanding of the events of the geological past. The aim of this work is to identify the bio-genic factor in the process of pseudo-morphogenesis in the shell sashes of the Early Silurian brachiopods from the car-bonate rocks of the Chernyshev Ridge. Structural and microscopic methods (Shimadzu XRD 6000; Fourier spectrometer InfraLum FT-02; JSM 6400 JEOL; VEGA3 TESCAN; MIN-8) were used to study quartz pseudomorphoses in the sashes of four shells of the Early Silurian brachiopods Borealis sр. of Pentamerida order from the carbonate strata of the Chernyshev Ridge. The salicification of the brachiopod shell walls resulted in the complete replacement of the original carbonate skeleton with a change in its structural organization. It is established that quartz is the main mineral component of the intra-shell material and secondary dolomite crystals and newly formed calcite aggregates. The paper discusses the participation of Early Paleozoic and modern cyanobacterial symbionts in the replacement of primary calcite with quartz and the formation of quartz crystalline aggregates on the shell walls. It is shown that quartz on the surface of shell sashes and in the intra-shell substance of brachiopods has undergone repeated transformations due to the combination of ancient and modern weathering processes.

Weighting of BLEG data with drainage and catchment properties to enhance Au anomalies

This research aims to take the effect of drainage sediment dilution into consideration by using catchment weighted-bulk leachable extractable gold (CW-BLEG) data in order to enhance and recognize Au anomalies. As a case study, an area in the Eskisehir region in Western Turkey was selected. In this area, gold-bearing crystalline quartz veins, of probable orogenic type, containing up to 20 g/t Au, occur in low-grade schists and marbles of the Karakaya Complex in the vicinity of the Sogut area. To classify the final geochemical maps of the BLEG data to differentiate Au anomalies from background, the singularity model was applied. After that, in order to take the sediments dilution effect (DE) into account, the other important factors in the study area such as the sinuosity index (SI) of the stream sediments per catchment, and the topography slope and area of each catchment were taken into consideration and implemented on the BLEG data. To do so, the CW-BLEG models based on the relation between the Au concentrations and each factor (i.e., C × sinuosity as DE-sinuosity, C × slope as DE-slope, and C × area as DE-area) were generated. Because of the insufficient number of known mineral deposits within the study area to evaluate the effectiveness of the models statistically, the models generated were compared with each other and studied using cross-validation. It demonstrated that the DE-area and DE-sinuosity models work better than the other model in recognizing strong and very strong anomalies considering the known mineral deposits. The cross-validation results show that the DE-area model provides a more robust result compared the other models. Considering the models generated, the very strong and strong Au anomalies in the western part of the study area are corresponded to the known gold mineralization (e.g., Sogut and Mayislar) hosted by the Karakaya Complex, and the anomalies in the eastern and central parts of the study area are associated with the Damdaca mineralization.

Copper-Containing Agates of the Avacha Bay (Eastern Kamchatka, Russia)

The copper-containing agates of the Avacha Bay (Eastern Kamchatka, Russia) have been investigated in this study. Optical microscopy, scanning electron microscopy, electron microprobe analysis, X-ray powder diffraction, Raman spectroscopy, and fluid inclusions were used to investigate the samples. It was found that copper mineralization in agates is represented by native copper, copper sulphides (chalcocite, djurleite, digenite, anilite, yarrowite, rarely chalcopyrite) and cuprite. In addition to copper minerals, sphalerite and native silver were also found in the agates. Native copper is localized in a siliceous matrix in the form of inclusions usually less than 100 microns in size—rarely up to 1 mm—forming dendrites and crystals of a cubic system. Copper sulphides are found in the interstices of chalcedony often cementing the marginal parts of spherule aggregates of silica. In addition, they fill the micro veins, which occupy a cross-cutting position with respect to the concentric bands of chalcedony. The idiomorphic appearance of native copper crystals and clear boundaries with the silica matrix suggest their simultaneous crystallization. Copper sulphides, cuprite, and barite micro veins indicate a later deposition. Raman spectroscopy and X-ray powder diffraction results demonstrated that the Avacha Bay agates contained cristobalite in addition to quartz and moganite. The fluid inclusions study shows that the crystalline quartz in the center of the nodule in agates was formed with the participation of solutions containing a very low salt concentration (<0.3 wt.% NaCl equivalent) at the temperature range 110–50 °C and below. The main salt components were CaCl2 and NaCl, with a probable admixture of MgCl2. The copper mineralization in the agates of the Avacha Bay established in the volcanic strata can serve as a direct sign of their metallogenic specialization.

Zeolite water purification at Tikal, an ancient Maya city in Guatemala

Evidence for the oldest known zeolite water purification filtration system occurs in the undisturbed sediments of the Corriental reservoir at the Maya city of Tikal, in northern Guatemala. The Corriental reservoir was an important source of drinking water at Tikal during the Late Preclassic to Late Classic cultural periods. X-ray diffraction analysis (XRD) and six AMS radiocarbon ages show that between ~ 2185 and 965 cal yr B.P. the drinking water in the Corriental reservoir water was filtered through a mixture of zeolite and coarse, sand-sized crystalline quartz. Zeolite is a non-toxic, three-dimensionally porous, crystalline, hydrated aluminosilicate with natural adsorbent and ion exchange properties, which removes harmful microbes as well as dispersed insoluble and soluble toxins from drinking water. The occurrence of zeolite in Corriental reservoir sediments expands our understanding of the earliest history of water purification and the long-term sustainability of an ancient Maya city.

Silicon and Aluminum Mobility in Soils of Jeju Island, Korea

The objective of the study is to investigate the effect of released silicon (Si) and aluminum (Al) during the formation of volcanic ash soil on the content of Si in groundwater on Jeju Island. Volcanic ash soils in Jeju Island were formed from pyroclastic materials that originated from basalt. We sampled four profiles, including basaltic bedrock of each soil series with large variations in elevation (160–320 m) and mean annual precipitation (MAP; 1,800–2,600 mm). The soil and bedrock minerals were analyzed for weathering of volcanic ash soils related to mineralogical transformations and mobility of Si and Al. Andisols (above 2,000 mm MAP) were dominantly composed of allophane and gibbsite. In Andisols used in the study, 10–70% of Si was lost, whereas the amount of Al was relatively conserved. This is because Al forms Al-humus complex and Andisols contain allophane. In contrast, non-Andisols located at low altitude with lower than 1,800 mm MAP were enriched with considerable amounts of Si and Al, because non-Andisols have crystalline clay minerals and quartz. These results indicate that Andisols, which are widely distributed in Jeju Island, may play an important role in contributing to the high concentration of dissolved Si in the groundwater.

Processing of mullite–glass ceramics using simplex-centroid design: Densification process dominated by liquid-phase sintering

Mullite is one of the preferred aluminosilicates for both traditional and advanced ceramics. This paper reports the use of simplex-centroid mixture design to prepare mullite–glass ceramics by reactive sintering. The phase composition and technological properties of formulations containing kaolinitic clay, kaolin waste and alumina were investigated after sintering at 1400°C. The sintering behavior was assessed by dilatometry. Microstructural analysis indicated the crystalline phases mullite, residual quartz, cristobalite, and α-alumina. A glassy phase was also identified as a matrix embedding mullite grains (as seen by X-ray diffractometry and scanning electron microscopy). In kaolin waste-rich formulations, a liquid phase sintering mechanism favored the densification process and the mechanical resistance. Highly significant statistical models allow correlating the concentrations of raw materials with linear firing shrinkage, water absorption and apparent porosity. Overall results stand out for the potential of using kaolin waste in the preparation of mullite–glass ceramics.

Modern Dielectric Materials for Output Windows of High-Power Microwave and Terahertz Sources

Analysis of dielectric properties of several materials, BN, AlN with BN additive, crystalline quartz, MgAl2O4 spinel, 6H-SiC in the millimeter and submillimeter (terahertz) ranges, is presented. Basing on the experimentally measured dielectric losses of these materials and on their thermal and mechanical properties, we made a calculation to estimate the maximal achievable output power that can be transmitted through disks made of such materials. Prospects for using these materials for gyrotron barrier window production are discussed.

Geochemical, palaeontological, and sedimentological approaches of a syn-orogenic clastic wedge: Implications for the provenance of the Permian (Cisuralian) Tunas Formation, Ventania System (Argentina)

The Tunas Formation crops out in the eastern sector of the Ventania System (southwestern Buenos Aires Province, Argentina) and represents the last unit of the Pillahuincó Group (Pennsylvanian–Cisuralian). This work integrates sedimentological, palaeontological, geochemical, and geochronological studies of the uppermost levels of the unit with the aim to enhance its palaeoenvironmental and stratigraphic framework within the Southwest Gondwana context. The analysed succession, of 250 m thick, is dominated by lithic arkoses and feldspathic litharenites composed of crystalline quartz and minor feldspars and volcanic fragments, interbedded with muddy-siltstones and heterolithic deposits with plant fossils. The succession is organized in three thickening- and coarsening-upward packages that correspond to fluvio-deltaic deposits. The plant fossil assemblage includes fronds of Gangamopteris obovata, Glossopteris angustifolia, Glossopteris wilsonii, and Asterotheca sp. cf. A. andersonii, in association with articulate ribbed stems of Paracalamites australis, which are here assigned to the Gangamopteris Zone. The low plant-diversity of the Tunas Formation could be related to the change from postglacial to semiarid-arid conditions evidenced during the Cisuralian in the Southwest Gondwana region where the study area is located. The obtained geochemical results indicate low recycling and sorting of continentally derived sediments with dominant input from the upper continental crust and acidic to intermediate magmatic precursors related to an active continental margin. Previous studies pointed out that the North Patagonian Massif, located SW of the Ventania System, was the source of such materials. Additionally, new LA-ICP-MS U–Pb zircon ages from two tuff levels of the Tunas Formation were considered together with previous U–Pb zircon ages. These suggest that the source of the ash fall deposits could be as far as the pre-Choiyoi volcanism (Late Mississippian–middle Cisuralian) of the Chilean Precordillera and Frontal Cordillera and as close as the Choiyoi volcanism (middle Cisuralian–Lower Triassic) of the Las Matras and Chadileuvú blocks, all located west of the Ventania System. The integrated analyses of the available U–Pb geochronological data also allowed us to constrain the sedimentation age of the uppermost levels of the Tunas Formation to the Artinskian. However, the age interval of the stratigraphic unit should be wider.

The effect of anisotropy on cross section spectra of quartz, calcite and corundum spheres of moderate size

Absorption, extinction and scattering cross section spectra of optically uniaxial materials are commonly described by the weighted sum approximation, also known as 1/3−2/3-approximation. Based on our previous work we investigate the deviations of infrared spectra calculated with the weighted sum approximation from cross sections generated by finite-difference time-domain (FDTD) simulations of crystalline calcite, quartz and corundum spheres. These materials are astronomically relevant and vary strongly concerning number, strength and resonance frequency of the transition dipole moments. Several effects of anisotropy were observed in the simulated spectra for both single particle spectra and orientation-averaged spectra, like shifted bulk modes and the appearance of additional peaks. These effects were not predicted by the weighted sum approximation.

Trace Level Detection and Quantification of Crystalline Silica in an Amorphous Silica Matrix with Natural Abundance 29Si NMR.

A protocol for the detection of trace amounts of quartz in amorphous silica gels by NMR spectroscopy was developed and tested on commercially available samples. Using natural abundance 29Si MAS NMR spectroscopy with CPMG acquisition and standard addition of crystalline quartz, quantitative detection of quartz concentrations down to 0.1% wt. was achieved. CPMG permitted to suppress the amorphous silica-derived signal, benefitting from the extremely long T2 relaxation time of quartz in 29Si and hence dramatically increasing the sensitivity. Dedicated post-processing exploiting the known CPMG spikelet frequencies allowed to probe the near-absence of quartz in commercial, 100% silica samples, enabling assessment of conformity of unknown samples to EU legislation (REACH).

Ablating nanoscale pores in crystalline quartz using laser-induced micro-plasmas in tri-layer structures

We demonstrate a novel approach for achieving rapid, consistent, and controllable micro-pore fabrication in single-crystalline quartz. These micro-pores are essential for applications in biology, i.e., studying ion channels in general and mechano-sensitive channels (MSC) in particular. The fabrication process consists of direct material ablation using pulsed UV light from a 193 nm excimer laser. These pulses ablate single-crystalline quartz chips by burning a laser-induced plasma in a tri-layer structure. Controllable plasma confinement and thus pore size is achieved by sandwiching a thin layer of a selected organic solution between the quartz chip and different substrates. This solution causes the confined micro-plasma to generate special ablation conditions, to create uniformly sized and shaped nanopores.

Dielectric polarizability of alkali and alkaline-earth modified silicate glasses at microwave frequency

The dielectric properties of alkali and alkaline earth-modified silicate glasses were characterized in the frequency range where electronic and ionic polarizabilities contribute to permittivity. From the Clausius–Mossotti (CM) model, dielectric polarizability of each cation-oxygen constituent was determined from the permittivity and molar volume. The silicon–oxygen polarizability of silica glass (5.24 Å3) is significantly higher than that of crystalline quartz (4.87 Å3), suggesting that additional polarization modes contribute to glass permittivity. A full range of alkali species (Li, Na, K, Rb, and Cs) were then added as glass network modifiers through a series of binary silicate glasses, and the silicon–oxygen polarizability increased to 5.38 Å3. A similar trend was observed for alkaline-earth aluminosilicate glasses in which the polarizability increased with the addition of cationic modifiers to 5.89 Å3. CM analysis provides a method to explore the fundamental relationship between the glass structure and its unique polarization response in the microwave frequency range. Microwave permittivity values are predicted over broad compositional ranges for alkali and alkaline earth-modified silicate glasses using the CM relationship.

Raman opalescence and central peak scattering near phase transition point in crystals

Comparison of isotemperature and isofrequency temperature dependences was used for revealing the soft mode behavior near phase transition points in ferroelectric and ferro-structural phase transitions in crystals. Sharp increase of the Raman scattering spectral intensity maximum near phase transition points was found and classified as soft mode Raman opalescence effect. Such phenomenon was observed in ferroelectric crystals LiNbO3, LiTaO3, and Pb5Ge3O11, and crystalline quartz. Presence of the high intensive and narrow central peak in low frequency area of light scattering spectra in vicinity of phase transition point was explained on the base of two coupled oscillator model.

Effect of phosphoric acid content on the microstructure and compressive strength of phosphoric acid-based metakaolin geopolymers

The phosphoric acid-based metakaolin geopolymers were prepared by regulating H3PO4/Al2O3 ratios. X-ray diffraction (XRD), thermogravimetry and differential scanning calorimeter (TG-DSC), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were used to determine the reaction process and phase formation. The results showed that the metakaolin calcined from Kaolinite mainly consisted of quartz crystalline phase and amorphous phase. The diffraction peak for quartz obviously became lower with the increasing of H3PO4/Al2O3 ratios. The excessive quartz from metakaolin did not totally take part in the chemical reaction. The polymeric structure of -P-O-Si-O-Al-O constitutes the main building block of phosphoric acid-based metakaolin geopolymeric structure. The optimized compressive strength was 29 ± 2 MPa with H3PO4/Al2O3 molar ratio = 1.3:1. The simulation of the total deformation under 29 MPa load and the total heat flux at 1400 °C of the phosphoric acid-based metakaolin geopolymers with H3PO4/Al2O3 molar ratio of 1.3:1 based on finite element method verified the failure mechanism and the excellent thermal stability at high temperature.

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

AbstractInfrared (IR) and Raman spectroscopic features of silicate glasses are often interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na2O]x[Al2O3]2[SiO2]98−x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order‐based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Thus, the bond length and angle distributions as well as Si–Qn species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF‐MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050‐1120 cm−1) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Qn speciation; and (c) assignment of the Raman bands in the 420‐600 cm−1 region to the bending modes of (SiO)n rings with different sizes (typically, n = 3‐6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF‐MD simulations. This finding invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.