Micro- and nano-size hydrogarnet clusters in calcium silicate garnet: Part II. Mineralogical, petrological, and geochemical aspects

2020 ◽  
Vol 105 (4) ◽  
pp. 468-478 ◽  
Author(s):  
Charles A. Geiger ◽  
George R. Rossman
Keyword(s):  
Calcium Silicate ◽  
Hydrogen Diffusion ◽  
Ir Absorption ◽  
Diffusion Behavior ◽  
Substitution Mechanism ◽  
And Behavior ◽  
First Time ◽  
Nano Size ◽  
Silicate Garnet ◽  
Thermal Stability Of

Abstract The nominally anhydrous, calcium-silicate garnets, grossular (Ca3Al2Si3O12), andradite (Ca3Fe23+Si3O12), schorlomite (Ca3Ti24+[Si,Fe23+]O12), and their solid solutions can incorporate structural OH-, often termed “water.” The IR single-crystal spectra of several calcium silicate garnets were recorded between 3000 and 4000 cm–1. Spectroscopic results are also taken from the literature. All spectra show various OH- stretching modes between 3500 and 3700 cm–1 and they are analyzed. Following the conclusions of Part I of this study, the garnets appear to contain local microscopic- and nano-size Ca3Al2H12O12- and Ca3Fe23+H12O12-like domains and/or clusters dispersed throughout an anhydrous “matrix.” The substitution mechanism is the hydrogarnet one, where (H4O4)4– ↔ (SiO4)4–, and various local configurations containing different numbers of (H4O4)4– groups define the cluster type. A single (H4O4) group is roughly 3 Å across and most (H4O4)-clusters are between this and 15 Å in size. This model can explain the IR spectra and also other experimental results. Various hypothetical “defect” and cation substitutional mechanisms are not needed to account for OH- incorporation and behavior in garnet. New understanding at the atomic level into published dehydration and H-species diffusion results, as well as H2O-concentration and IR absorption-coefficient determinations, is now possible for the first time. End-member synthetic and natural grossular crystals can show similar OH- “band patterns,” as can different natural garnets, indicating that chemical equilibrium could have operated during their crystallization. Under this assumption, the hydrogarnet-cluster types and their concentrations can potentially be used to decipher petrologic (i.e., P-T-X) conditions under which a garnet crystal, and the rock in which it occurs, formed. Schorlomites from phonolites contain no or very minor amounts of H2O (0.0 to 0.02 wt%), whereas Ti-bearing andradites from chlorite schists can contain more H2O (∼0.3 wt%). Different hydrogarnet clusters and concentrations can occur in metamorphic grossulars from Asbestos, Quebec, Canada. IR absorption coefficients for H2O held in hydrogrossularand hydroandradite-like clusters should be different in magnitude and this work lays out how they can be best determined. Hydrogen diffusion behavior in garnet crystals at high temperatures is primarily governed by the thermal stability of the different local hydrogarnet clusters at 1 atm.

Micro- and nano-size hydrogarnet clusters and proton ordering in calcium silicate garnet: Part I. The quest to understand the nature of “water” in garnet continues

2020 ◽  
Vol 105 (4) ◽  
pp. 455-467 ◽  
Author(s):  
Charles A. Geiger ◽  
George R. Rossman
Keyword(s):  
Calcium Silicate ◽  
Room Temperature ◽  
Experimental Investigations ◽  
Chemical Models ◽  
Substitution Mechanism ◽  
Coupled Substitution ◽  
Cluster Type ◽  
Nano Size ◽  
Silicate Garnet ◽  
Proton Ordering

Abstract The calcium-silicate garnets, grossular (Ca3Al2Si3O12), andradite (Ca3Fe23+Si3O12), and their solid solutions [Ca3(Alx,Fe1−x3+)2Si3O12], can incorporate various amounts of structural OH–. This has important mineralogical, petrological, rheological, and geochemical consequences and extensive experimental investigations have focused on the nature of “water” in these phases. However, it was not fully understood how OH- was incorporated and this has seriously hampered the interpretation of different research results. IR single-crystal spectra of several nominally anhydrous calcium silicate garnets, both “end-member” and solid-solution compositions, were recorded at room temperature and 80 K between 3000 and 4000 cm–1. Five synthetic hydrogarnets in the system Ca3Al2(SiO4)3-Ca3Al2(H4O4)3-Ca3Fe23+(SiO4)3-Ca3Fe23+(H4O4)3 were also measured via IR ATR powder methods. The various spectra are rich in complexity and show several OH- stretching modes at wavenumbers between 3500 and 3700 cm–1. The data, together with published results, were analyzed and modes assigned by introducing atomic-vibrational and crystal-chemical models to explain the energy of the OH- dipole and the structural incorporation mechanism of OH-, respectively. It is argued that OH- is located in various local microscopic- and nano-size Ca3Al2H12O12- and Ca3Fe23+H12O12-like clusters. The basic substitution mechanism is the hydrogarnet one, where (H4O4)4– ↔ (SiO4)4–, and various local configurations containing different numbers of (H4O4)4– groups define the cluster type. Some spectra also possibly indicate the presence of tiny hydrous inclusion phases, as revealed by OH- modes above about 3670 cm–1. They were not recognized in earlier studies. Published proposals invoking different hypothetical “defects” and coupled-substitution mechanisms involving H+ are not needed to interpret the IR spectra, at least for OH- modes above about 3560 cm–1. Significant mineralogical, petrological, and geochemical consequences result from the analysis and are discussed in the accompanying Part II (this issue) of the investigation.

The role of pathos: from argumentative responses to feeling and emotions

2017 ◽  
Author(s):  
Michel Meyer
Keyword(s):  
Short Distance ◽  
Social World ◽  
Legal Rhetoric ◽  
Law And Politics ◽  
The Social ◽  
And Behavior ◽  
First Time

Chapter 10 is devoted to the role of emotions or pathos. Pathos was the term ordinarily used to denote the notion of audience. For the first time since Aristotle, emotions receive a full role in a treatise on rhetoric. The responses of the audience are modulated by its emotions. What is their nature and how precisely do they operate? The areas of political and legal rhetoric are examined here in the light of an original view of the theory of distance: values at greater distance become passions at short distance, and this is one of the features which demarcates politics from law. Law and politics are not merely argumentative, nor are they entirely emotional. The norms they codify are often implicit in their shaping of our mutual expectations and behavior in the social world.

scholarly journals First thermal studies on visible-light-switchable negative T-type photochromes of a nitrile-rich series

RSC Advances ◽  
2021 ◽  
Vol 11 (34) ◽  
pp. 21097-21103
Author(s):  
Mikhail Yu. Belikov ◽  
Mikhail Yu. Ievlev
Keyword(s):  
Thermal Stability ◽  
Visible Light ◽  
Temperature Effect ◽  
Thermal Studies ◽  
First Time ◽  
Thermal Stability Of

The temperature effect on the thermal stability of both the initial and photoinduced forms of nitrile-rich T-type photochromes was studied for the first time.

scholarly journals Internal melt figures in ice by rapid adiabatic compression

1994 ◽  
Vol 40 (134) ◽  
pp. 132-134
Author(s):  
R.E. Gagnon ◽  
C. Tulk ◽  
H. Kiefte
Keyword(s):  
Phase Transformations ◽  
Grain Boundaries ◽  
Single Crystals ◽  
Adiabatic Compression ◽  
Air Bubbles ◽  
Water Ice ◽  
Deep Focus ◽  
And Behavior ◽  
First Time

AbstractSingle crystals and bicrystals of water ice have been adiabatically pressurized to produce, and clearly illustrate, two types of internal melt figures: (1) dendritic figures that grow from nucleation imperfections on the specimen’s surface, or from air bubbles at grain boundaries, into the ice as pressure is elevated; and (2) compression melt fractures, flat liquid-filled disks, that nucleate at imperfections in the crystal and grow with the application of pressure eventually to sprout dendritic fingers at the periphery. The transparency of the ice permitted visualization of the growth and behavior of the figures, and this could be an important tool in understanding the role of phase transformations in deep-focus earthquakes. Correlation between figure size and pressure is noted for the first time.

Thermal Breakdown Kinetics of 1-Ethyl-3-Methylimidazolium Ethylsulfate Measured Using Quantitative Infrared Spectroscopy

2017 ◽  
Vol 71 (12) ◽  
pp. 2626-2631 ◽  
Author(s):  
Jeffrey L. Wheeler ◽  
McKinley Pugh ◽  
S. Jake Atkins ◽  
Jason M. Porter
Keyword(s):  
Thermal Stability ◽  
Room Temperature ◽  
Computational Models ◽  
Elevated Temperatures ◽  
Molar Absorptivity ◽  
Ir Absorption ◽  
Optical Cell ◽  
Multiple Samples ◽  
Kinetics Of ◽  
Thermal Stability Of

In this work, the thermal stability of the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO4]) is investigated using infrared (IR) spectroscopy. Quantitative IR absorption spectral data are measured for heated [EMIM][EtSO4]. Spectra have been collected between 25 ℃ and 100 ℃ using a heated optical cell. Multiple samples and cell pathlengths are used to determine quantitative values for the molar absorptivity of [EMIM][EtSO4]. These results are compared to previous computational models of the ion pair. These quantitative spectra are used to measure the rate of thermal decomposition of [EMIM][EtSO4] at elevated temperatures. The spectroscopic measurements of the rate of decomposition show that thermogravimetric methods overestimate the thermal stability of [EMIM][EtSO4].

Meyer-Neldel Rule on thermal stability parameters (trap depth and frequency factor) of luminescence signals in quartz

2021 ◽  
Author(s):  
Zuzanna Kabacińska ◽  
Alida Timar-Gabor ◽  
Benny Guralnik
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Hydrogen Diffusion ◽  
Dose Range ◽  
Accurate Determination ◽  
Frequency Factor ◽  
Proton Conduction ◽  
High Dose ◽  
Compensation Law ◽  
Thermal Stability Of

<p>Thermally activated processes can be described mathematically by the Arrhenius equation. The Meyer-Neldel Rule (MNR), or compensation law, linearly relates the pre-exponent term to the logarithm of the excitation enthalpy for processes that are thermally driven in an Arrhenian manner. This empirical rule was observed in many areas of materials science, in physics, chemistry, and biology. In geosciences it was found to uphold in hydrogen diffusion (Jones 2014a) and proton conduction (Jones 2014b) in minerals.</p><p>Trapped charge dating methods that use electron spin resonance (ESR) or optically or thermally stimulated luminescence (OSL and TL) are based on the dose-dependent accumulation of defects in minerals such as quartz and feldspar. The thermal stability of these defects in the age range investigated is a major prerequisite for accurate dating, while the accurate determination of the values of the trap depths and frequency factors play a major role in thermochronometry applications. </p><p>The correlation of kinetic parameters for diffusion has been very recently established for irradiated oxides (Kotomin et al. 2018). A correlation between the activation energy and the frequency factor that satisfied the Meyer–Neldel rule was reported when the thermal stability of [AlO<sub>4</sub>/h<sup>+</sup>]<sup>0</sup> and [TiO<sub>4</sub>/M<sup>+</sup>]<sup>0</sup> ESR signals in quartz was studied as function of dose (Benzid and Timar-Gabor 2020). Here we compiled the optically stimulated luminescence (OSL) data published so far in this regard, and investigated experimentally the thermal stability of OSL signals for doses ranging from 10 to 10000 Gy in sedimentary quartz samples. We report a linear relationship between the natural logarithm of the preexponent term (the frequency factor) and the activation energy E, corresponding to a Meyer-Neldel energy of 45 meV, and a deviation from first order kinetics in the high dose range accompanied by an apparent decrease in thermal stability. The implications of these observations and the atomic and physical mechanisms are currently studied.</p><p> </p><p><strong>References</strong></p><p>Benzid, K., Timar Gabor, A. 2020. The compensation effect (Meyer–Neldel rule) on [AlO<sub>4</sub>/h<sup>+</sup>]<sup>0</sup> and [TiO<sub>4</sub>/M<sup>+</sup>]<sup>0</sup> paramagnetic centers in irradiated sedimentary quartz. <em>AIP Advance</em>s 10, 075114.</p><p>Kotomin, E., Kuzovkov, V., Popov, A. I., Maier, J., and Vila, R. 2018. Anomalous kinetics of diffusion-controlled defect annealing in irradiated ionic solids. <em>J. Phys. Chem. A</em> 122(1), 28–32</p><p>Jones, A. G. (2014a), Compensation of the Meyer-Neldel Compensation Law for H diffusion in minerals, <em>Geochem. Geophys. Geosyst.</em>, 15, 2616–2631</p><p>Jones, A. G. (2014b), Reconciling different equations for proton conduction using the Meyer-Neldel compensation rule, <em>Geochem. Geophys. Geosyst</em>., 15, 337–349</p>

Proton NMR Studies of Hydrogen Diffusion Behavior for ZrBe2H1.4*

1992 ◽  
Vol 1 (1) ◽  
pp. 725-730
Author(s):  
R. C. Bowman ◽  
D. R. Torgeson ◽  
A. J. Maeland
Keyword(s):  
Hydrogen Diffusion ◽  
Proton Nmr ◽  
Nmr Studies ◽  
Diffusion Behavior

Investigation of hydrogen diffusion behavior in 12Cr2Mo1R(H) steel by electrochemical tests and first-principles calculation

2021 ◽  
Vol ahead-of-print (ahead-of-print) ◽  
Author(s):  
Xiang Qiu ◽  
Kun Zhang ◽  
Qin Kang ◽  
Yicheng Fan ◽  
Hongyu San ◽  
...  
Keyword(s):  
Activation Energy ◽  
Diffusion Coefficient ◽  
Hydrogen Atom ◽  
Hydrogen Embrittlement ◽  
First Principles ◽  
Hydrogen Diffusion ◽  
First Principles Calculations ◽  
Content Type ◽  
Diffusion Behavior ◽  
Hydrogen Diffusion Coefficient

Purpose This paper aims to study the mechanism of hydrogen embrittlement in 12Cr2Mo1R(H) steel, which will help to provide valuable information for the subsequent hydrogen embrittlement research of this kind of steel, so as to optimize the processing technology and take more appropriate measures to prevent hydrogen damage. Design/methodology/approach The hydrogen diffusion coefficient of 12Cr2Mo1R(H) steel was measured by the hydrogen permeation technique of double electrolytic cells. Moreover, the influence of hydrogen traps in the material and experimental temperature on hydrogen diffusion behavior was discussed. The first-principles calculations based on density functional theory were used to study the occupancy of H atoms in the bcc-Fe cell, the diffusion path and the interaction with vacancy defects. Findings The results revealed that the logarithm of the hydrogen diffusion coefficient of the material has a linear relationship with the reciprocal of temperature and the activation energy of hydrogen atom diffusion in 12Cr2Mo1R(H) steel is 23.47 kJ/mol. H atoms stably exist in the nearly octahedral interstices in the crystal cell with vacancies. In addition, the solution of Cr/Mo alloy atom does not change the lowest energy path of H atom, but increases the diffusion activation energy of hydrogen atom, thus hindering the diffusion of hydrogen atom. Cr/Mo and vacancy have a synergistic effect on inhibiting the diffusion of H atoms in α-Fe. Originality/value This article combines experiments with first-principles calculations to explore the diffusion behavior of hydrogen in 12Cr2Mo1R(H) steel from the macroscopic and microscopic perspectives, which will help to establish a calculation model with complex defects in the future.

Description of the mature larva and pupa of Ora semibrunnea Pic (Coleoptera: Scirtidae) with notes on its biology

Zootaxa ◽  
2019 ◽  
Vol 4551 (1) ◽  
pp. 53 ◽  
Author(s):  
GABRIELLE JORGE ◽  
MARÍA LAURA LIBONATTI ◽  
CESAR JOÃO BENETTI ◽  
NEUSA HAMADA
Keyword(s):  
Water Surface ◽  
Brazilian Amazon ◽  
First Record ◽  
Biological Information ◽  
Mature Larva ◽  
Natural Lakes ◽  
Morphological Adaptations ◽  
Brazilian Amazon Region ◽  
And Behavior ◽  
First Time

In this paper we describe and illustrate for the first time the immature forms (larva and pupa) of Ora semibrunnea Pic, 1922, including biological information and behavior observed in the laboratory. This is the first record of the occurrence of this species in the Brazilian Amazon region. Larvae and pupae were found in natural lakes associated with macrophyte banks. Pupae are aquatic and have morphological adaptations (well-developed pronotal siphons) to obtain atmospheric O2 at the water surface. 

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