scholarly journals The Formation of Barite and Celestite through the Replacement of Gypsum

Minerals ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 189 ◽  
Author(s):  
Pablo Forjanes ◽  
José Astilleros ◽  
Lurdes Fernández-Díaz
Keyword(s):  
Solid Solution ◽  
Fluid Phase ◽  
Secondary Phase ◽  
Crystal Habit ◽  
Replacement Reaction ◽  
Random Orientation ◽  
End Members ◽  
Kinetics Of ◽  
Oriented Layer ◽  
Orientational Relationship

Barite (BaSO4) and celestite (SrSO4) are the end-members of a nearly ideal solid solution. Most of the exploitable deposits of celestite occur associated with evaporitic sediments which consist of gypsum (CaSO4·2H2O) or anhydrite (CaSO4). Barite, despite having a broader geological distribution is rarely present in these deposits. In this work, we present an experimental study of the interaction between gypsum crystals and aqueous solutions that bear Sr or Ba. This interaction leads to the development of dissolution-crystallization reactions that result in the pseudomorphic replacement of the gypsum crystals by aggregates of celestite or barite, respectively. The monitoring of both replacement reactions shows that they take place at very different rates. Millimeter-sized gypsum crystals in contact with a 0.5 M SrCl2 solution are completely replaced by celestite aggregates in less than 1 day. In contrast, only a thin barite rim replaces gypsum after seven days of interaction of the latter with a 0.5 M BaCl2 solution. We interpret that this marked difference in the kinetics of the two replacement reactions relates the different orientational relationship that exists between the crystals of the two replacing phases and the gypsum substrate. This influence is further modulated by the specific crystal habit of each secondary phase. Thus, the formation of a thin oriented layer of platy barite crystals effectively armors the gypsum surface and prevents its interaction with the Ba-bearing solution, thereby strongly hindering the progress of the replacement reaction. In contrast, the random orientation of celestite crystals with respect to gypsum guarantees that a significant volume of porosity contained in the celestite layer is interconnected, facilitating the continuous communication between the gypsum surface and the fluid phase and guaranteeing the progress of the gypsum-by-celestite replacement.

Rapid exsolution behaviour in the bornite–digenite series, and implications for natural ore assemblages

1999 ◽  
Vol 63 (1) ◽  
pp. 1-12 ◽  
Author(s):  
B. A. Grguric ◽  
A. Putnis
Keyword(s):  
Solid Solution ◽  
Bulk Composition ◽  
Quenching Process ◽  
Limited Degree ◽  
Diffusion Rates ◽  
Diffraction Patterns ◽  
Rapid Kinetics ◽  
End Members ◽  
Kinetics Of ◽  
Degree Of Order

AbstractIntermediate compositions along the bornite–digenite join exsolve during quenching from above-solvus temperatures. This involves vacancy clustering and cation ordering processes, and is facilitated by fast cation diffusion rates in the presence of a large (10–25%) metal vacancy population. Samples of six different compositions across the bornite–Cu9S5 join, synthesised from component elements in sealed quartz capsules, were water-quenched from 600°C and analysed using high-resolution neutron powder diffraction (HRPD). Time-of-flight spectra measured at room temperature showed all intermediate compositions had exsolved into mixtures of bornite and low digenite with a 5.0a superstructure. No evidence for the presence of any other phase was found. Variations in the lattice parameters of the exsolved bornite phase were observed for different bulk compositions across the join, and ascribed to variations in the degree of order. Bornite exsolved from digenite-rich compositions may not be fully ordered due to the much lower solvus temperatures at the Cu-rich end of the solid solution. As only slight differences were observed between the diffraction patterns of a visibly exsolved and a rapidly quenched sample of the same bulk composition, the formation of optically-visible exsolution lamellae on {100} is ascribed to a process of coalescence of sub-microscopic domains initially formed during the quenching process. The rapid kinetics of exsolution at geologically low temperatures, explains the lack of authenticated natural occurrences of intermediate compositions in the solid solution in nature, and the limited degree of stoichiometric variation observed in end-members.

scholarly journals Oxidation behavior of non-stoichiometric (Zr,Hf,Ti)Cx carbide solid solution powders in air

2021 ◽  
Author(s):  
Huilin Lun ◽  
Yi Zeng ◽  
Xiang Xiong ◽  
Ziming Ye ◽  
Zhongwei Zhang ◽  
...  
Keyword(s):  
Solid Solution ◽  
Oxidation Resistance ◽  
Oxidation Behavior ◽  
Group Iv ◽  
Hypersonic Vehicles ◽  
Metal Carbides ◽  
Initial Oxidation ◽  
Plasma Sintering ◽  
Spark Plasma ◽  
Kinetics Of

AbstractMulti-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles. However, for group IV transition-metal carbides, the oxidation behavior of multi-component non-stoichiometric (Zr,Hf,Ti)Cx carbide solid solution has not been clarified yet. The present work fabricated four kinds of (Zr,Hf,Ti)Cx carbide solid solution powders by free-pressureless spark plasma sintering to investigate the oxidation behavior of (Zr,Hf,Ti)Cx in air. The effects of metallic atom composition on oxidation resistance were examined. The results indicate that the oxidation kinetics of (Zr,Hf,Ti)Cx are composition dependent. A high Hf content in (Zr,Hf,Ti)Cx was beneficial to form an amorphous Zr-Hf-Ti-C-O oxycarbide layer as an oxygen barrier to enhance the initial oxidation resistance. Meanwhile, an equiatomic ratio of metallic atoms reduced the growth rate of (Zr,Hf,Ti)O2 oxide, increasing its phase stability at high temperatures, which improved the oxidation activation energy of (Zr, Hf, Ti)Cx.

scholarly journals (Ti,Cr)C-Based Cermets with Varied Nicr Binder Content via Elemental SHS for Perspective Cutting Tools

Crystals ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 412
Author(s):  
Stepan Vorotilo ◽  
Philipp V. Kiryukhantsev-Korneev ◽  
Boris S. Seplyarskii ◽  
Roman A. Kochetkov ◽  
Nail I. Abzalov ◽  
...  
Keyword(s):  
Solid Solution ◽  
Gas Permeability ◽  
Combustion Velocity ◽  
Cutting Tools ◽  
Secondary Phase ◽  
Fold Increase ◽  
Combustion Products ◽  
Secondary Phase Formation ◽  
Secondary Reactions ◽  
Nickel Binder

The effects of granulation of reactive mixtures Ti-Cr-C and Ti-Cr-C-Ni on the combustion temperature and velocity, as well as phase composition and mechanical properties (crushing ability) of combustion products, were studied. Granulation was associated with a 1.5-fold increase in combustion velocity, caused by a nearly 10-fold increase in gas permeability. Secondary reactions between TiC, Cr7C3, and molten Ni led to the formation of (Ti,Cr)C FCC solid solution and Ni2.88Cr1.12 intermetallics. After the combustion of Ti-Cr-C-Ni mixtures, prolonged fluorescence was registered, suggesting the exothermic nature of secondary phase formation reactions. The introduction of the nickel binder decreased the content of Cr in the solid solution (Ti,Cr)C owing to the formation of the Ni2.88Cr1.12 phase. To prevent the Cr depletion from the carbide solid solution, Ni-20%Cr binder was added to the granulated 80%(Ti + C)/20%(3Cr + 2C) mixture. Combustion of granulated mixture yielded brittle porous sinter cake, which was easy to crush and mill, whereas the combustion products from the powdered mixtures were more ductile and harder to crush.

Kinetic Assessment of the Dry Reforming of Methane over a Solid Solution Ni–La Oxide Catalyst

2021 ◽  
Author(s):  
Victor Stivenson Sandoval-Bohorquez ◽  
Edgar M. Morales-Valencia ◽  
Carlos Omar Castillo-Araiza ◽  
Luz Marina Ballesteros Rueda ◽  
Víctor Gabriel Baldovino Medrano
Keyword(s):  
Solid Solution ◽  
Active Sites ◽  
Oxide Catalyst ◽  
Bond Cleavage ◽  
Scale Up ◽  
Active Surface ◽  
Dry Reforming ◽  
Dry Reforming Of Methane ◽  
Nickel Surface ◽  
Kinetics Of

The dry reforming of methane is a promising technology for the abatement of CH<sub>4</sub> and CO<sub>2</sub>. Solid solution Ni–La oxide catalysts are characterized by their long–term stability (100h) when tested at full conversion. The kinetics of dry reforming over this type of catalysts has been studied using both power law and Langmuir–Hinshelwood based approaches. However, these studies typically deal with fitting the net CH<sub>4</sub> rate hence disregarding competing and parallel surface processes and the different possible configurations of the active surface. In this work, we synthesized a solid solution Ni–La oxide catalyst and tested six Langmuir–Hinshelwood mechanisms considering both single and dual active sites for assessing the kinetics of dry reforming and the competing reverse water gas shift reaction and investigated the performance of the derived kinetic models. In doing this, it was found that: (1) all the net rates were better fitted by a single–site model that considered that the first C–H bond cleavage in methane occurred over a <a>metal−oxygen </a>pair site; (2) this model predicted the existence of a nearly saturated nickel surface with chemisorbed oxygen adatoms derived from the dissociation of CO<sub>2</sub>; (3) the dissociation of CO<sub>2</sub> can either be an inhibitory or an irrelevant step, and it can also modify the apparent activation energy for CH<sub>4</sub> activation. These findings contribute to a better understanding of the dry reforming reaction's kinetics and provide a robust kinetic model for the design and scale–up of the process.

Chemistry and microstructure of orthoamphiboles from cordierite-amphibole rocks at Outokumpu, North Karelia, Finland

1982 ◽  
Vol 45 (337) ◽  
pp. 55-62 ◽  
Author(s):  
Peter J. Treloar ◽  
Andrew Putnis
Keyword(s):  
Solid Solution ◽  
Electron Microprobe ◽  
Fluid Phase ◽  
External Control ◽  
Solid Solution Series ◽  
Solution Series

AbstractOrthoamphiboles from the cordierite-amphibole-bearing rocks at Outokumpu span a large part of the gedrite-anthophyllite solid-solution series. The amphiboles grew at temperatures near to or just above that of the solvus crest with post-metamorphic cooling resulting in sub-solvus exsolution, the distribution of which is compatible with an asymmetric solvus in which the anthophyllite limb is the steeper. Metamorphic conditions in the area imply that the crest of the solvus is unlikely to be at a temperature in excess of about 600 °C Electron microprobe traverses and Al-Kα scans show that the amphibole compositions vary rapidly both along and across grains. These variations can be explained by varying availability of Na controlling the extent of the edenitic substitution in the solid solution series. In this case this variability in Na availability may be explained by the external control of μNa through the fluid phase.

Oxidation Behavior of Ta-W Alloy

2020 ◽  
Vol 993 ◽  
pp. 299-306
Author(s):  
Jia Xin Li ◽  
Yu Hong Chen ◽  
Zhang Jun Bai ◽  
Shuai Du ◽  
Lan Er Wu
Keyword(s):  
Solid Solution ◽  
Coefficient Of Thermal Expansion ◽  
Complex Oxide ◽  
Tungsten Alloy ◽  
Good Effect ◽  
Initial Oxidation ◽  
Compressive Stresses ◽  
Initial Stage ◽  
Kinetics Of ◽  
Oxidation Behaviors

The oxidation behaviors of tantalum-tungsten alloy with 10-20% W was investigated between temperature range of 700 to 900 °C exposed in air. The kinetics of Ta-W alloy was determined by TG-DTA, the characteristics of oxides were analyzed by SEM, EDS and XRD. The oxidation tests revealed that the alloys obeyed parabolic kinetic in the initial stage, then translated in linear law. The addition of W has a good effect on the oxidation resistance of Ta-W alloys at experimental temperature. Solid solution of Ta2O5 form in case of oxidation product of Ta-10W, Ta-15W alloys, while the complex oxide Ta22W4O67 form after Ta-20W alloy oxidized. The formation of solid solution and complex oxide impeded the volatilization. The compact oxide film protects the penetration of oxygen in the initial oxidation stage. The large compressive stresses and mismatch of the coefficient of thermal expansion between oxide scale and matrix alloys make the oxides layer be broken, which cause kinetic of oxidization obeying linear law.

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