Al Substitution Research Articles

Atomistic Mechanism of Al Substitution Effects on the Ferroelastic Post-stishovite Transition by High-Pressure Single-Crystal X-Ray Diffraction

Atomistic Mechanism of Al Substitution Effects on the Ferroelastic Post-stishovite Transition by High-Pressure Single-Crystal X-Ray Diffraction

Specifics of Al substitution into boron carbide: A DFT study

Boron carbide (B4C), known for its hardness and low density, is prone to local amorphization under high non-hydrostatic loads, limiting its applications. Aluminum doping is promising due to aluminum's atomic size, fitting into the B4C crystal lattice, particularly the intericosahedra chain, potentially reducing amorphization. This work uses first-principles calculations to study aluminum placement in B4C. We examine the potential for Al substitution in the icosahedron and intericosahedra chain, identifying possible locations. Results show that aluminum can't replace atoms in the icosahedron, but substituting one central atom in the intericosahedra chain with aluminum is energetically favorable and likely changes the chain configuration to an angular one. Additionally, aluminum can substitute one carbon in the (C-B-C) chain of B12(C-B-C) boron carbide. Comparative analysis suggests these configurations may coexist. Our study offers a theoretical model that can guide future experimental efforts and provides valuable insights into the structural specifics of aluminum-doped boron carbide.

Tailoring electronic structure and thermodynamic stability of (Al, In)-substituted GaAs: Ab-initio insights into bulk and (001) surfaces

Ab-initio calculations are conducted to investigate the structural properties, electronic structure, and thermodynamic stabilities of bulk and (001) surface systems of the GaAs semiconductor in its zinc-blende crystal phase. For the bulk case, we focus on the impact of substituting gallium atoms with M atoms (M = Al, In) at various concentrations (5.55 %, 11 %, and 22 %). We present the resulting structural parameters, along with the formation and substitutional energies associated with these substitutions. For surface systems, we explore indium (In) or aluminum (Al) substitutions at coverages of 0.25, 0.50, and 1.0 monolayers. This includes investigating the effects of substituting M atoms within the first atomic layer of the slabs. Ab-initio thermodynamic calculations reveal that high Al substitutions, in both bulk and surface, result in more favorable formation and surface energies. In contrast, In substitutions exhibit the opposite behavior, with increasing In content leading to less favorable energetics. Moreover, density of states analysis reveals that bulk systems maintained a semiconducting character, while all studied surface configurations exhibited a metallic electronic behavior. This study provides valuable insights into the influence of Al and In substitutions on the structural, electronic, and thermodynamic properties of GaAs, both in bulk and on the (001) surface.

Electromagnetic wave absorption properties of La-Ca-Co-Al substituted M-type Sr-hexaferrite-rubber sheets in 50–75 GHz range

This study reports on the electromagnetic (EM) wave absorption characteristics of M-type hexaferrite-rubber sheets, where Al was additionally substituted into high-performance permanent magnet compositions, Sr0.2La0.4Ca0.4Co0.25Fe9.75-xAlxO19-d (LCCA-SrM, x = 0, 0.2, 0.4). While non-substituted SrFe12O19 powder-rubber sheet had a ferromagnetic resonance frequency (fFMR) of 48.5 GHz, the LCCA-SrM (x = 0, 0.2, 0.4) rubber sheets showed increased fFMR values of 63.3, 66.2, and 68.5 GHz, respectively, with the increasing x values. The frequency of minimum reflection loss (fRLmin) also increased correspondingly with the change in fFMR. This significant increase in fFMR and fRLmin is attributed to the greatly enhanced magnetocrystalline anisotropy from the La-Ca-Co substitution in SrM and the incremental increase in magnetic anisotropy field (Hani) due to Al substitution. The absorption band (Δf) satisfying RL < −10 dB, was 45.0–53.4 GHz for SrM, and 52.9–75, 50–75, and 59–74.2 GHz for the x = 0, 0.2, and 0.4 samples, respectively. The x = 0.2 sheets demonstrated the widest absorption, covering 50–75 GHz. This study is highly promising as it is the first to demonstrate the feasibility of developing an EM wave absorber sheet for frequencies above 50 GHz using hexaferrite powder synthesized via the solid-state method, which offers scalability and cost-efficiency for mass production.

Nanoporous CoFe2O4 with inherited cation doping from matrix realizing ultra-stable alkaline hydrogen evolution for over 1000 hours

Spinel-type oxides have been acknowledged for their eminent catalytic ability towards alkaline hydrogen evolution reaction (HER) due to the special metal occupying structures. To further improve conductivity, inherited cation doped spinel has been rapidly synthesized via scalable alloying-dealloying strategy. Specially, the resultant Al-doped CoFe2O4 possesses typical bi-continuous pore-ligament structure, showing a huge surface area for electrocatalysis. It only demands HER overpotentials of 22.9 and 275 mV to achieve 10 and 100 mA cm-2, respectively. Furthermore, it also exhibits ultra-stable hydrogen evolution for 1000 h Under the industrial conditions (6 M KOH, 60 °C), Al-CoFe2O4 || RuO2 couple just needs 1.75 V to reach high current density of 500 mA cm-2 and could steadily produce hydrogen for over 50 h with merely 8 % voltage loss. Theoretical calculation confirms that Al substitution could indeed increase valence electron concentration. Based on this optimized configuration, H2O molecule is preferred to adsorb on Co site and conducive to dissociate into *OH-*H co-adsorption. And thus, the energy barrier of alkaline HER can be reduced to 0.98 eV on Al-doping CoFe2O4 model. To further clarify the active species derived from HER, operando X-ray diffraction and Fourier transform infrared are used to prove that the superficial CoFe2O4 has been transformed into more active CoOOH/FeOOH. This work offers a guide to facilely fabricate cost-effective HER catalysts that are suitable for industrial hydrogen production.

Effects of Sm2O3 and TiO2 on the performance of MgAl2O4-Si3N4 ceramics for solar thermal absorber in concentrating solar power

Aiming to further improve the properties of novel MgAl2O4-Si3N4 ceramic used as solar thermal absorbing material in concentrating solar power, effects of Sm2O3 and TiO2 on performance of the composites were investigated especially the mechanisms of different additives on microstructure and high temperature stability. The results show that both additives can accelerate sintering, reduce sintering temperature, improve the density and high temperature stability via liquid phase sintering mechanism. Besides, TiO2 can form displacement solid solution with Al2O3 to promote the sintering process. Sm2O3 is more conducive to improving the bending strength due to its function of increasing the length diameter ratio of β-Si3N4. TiO2 is more favorable for improving solar absorption owing to the distinctive absorption spectrum and large number of cation vacancy caused by substitution of Al3+ by Ti4+. MgAl2O4-Si3N4 composites with Sm2O3 and TiO2 additives have better performance than MgAl2O4-Si3N4, Si3N4 and SiC ceramics prepared via the same procedure, which makes it a certain choice for solar thermal absorbing material.

Effect of Al substitution on the electron-phonon interaction for β-Ga2O3

The relevant parameters of electron–phonon (e-ph) interaction, like mean phonon temperature and e-ph interaction strength for Al-substituted β-Ga2O3, i.e., β-(AlxGa1–x)2O3 alloys, have been determined from the fitting of the temperature dependence of the band gap using Bose–Einstein empirical model. Both e-ph interaction strength and mean phonon temperature decrease sharply for initial Al compositions; then, they increase slightly and become more or less constant. This is explained by using the already existed concepts of propagon and diffuson for the phonon modes that interact with the electrons. Presence of two sublattices at the local level is found to be the origin of diffuson-like behaviour of phonon modes in β-(AlxGa1–x)2O3 alloyed system, which vibrate independently like a non-propagating oscillator and diffuse through the β-(AlxGa1–x)2O3 lattice. The diffuson-like behaviour of phonon modes in the β-(AlxGa1–x)2O3 alloy is found to be responsible for the reduction in e-ph interaction. The reduction of e-ph interaction strength of β-Ga2O3 with Al substitution may lead to the better performance of power devices working at higher temperatures.

Stability and transformation of jarosite and Al-substituted jarosite in an acid sulfate paddy soil under laboratory and field conditions

Jarosite, a prominent mineral in oxidised acid sulfate soil, is known to sorb and incorporate a variety of elements, including Al. However, to understand the role that jarosite plays in regulating element cycles, it is crucial to understand the stability and transformation pathways of jarosite in an acid sulfate soil under dynamic biogeochemical conditions. In this study, we observed the transformation of unsubstituted jarosite and Al-substituted jarosite, collectively referred to as ‘jarosite’, in an acid-sulfate rice paddy topsoil and subsoil from Thailand. Jarosite was incubated in flooded paddy topsoils and subsoils for up to sixteen weeks, both in laboratory mesocosms and in the field, using bags made of polyethylene terephthalate mesh. One set of mesh bags contained jarosite that was not mixed with any other minerals, and referred to as ‘pure mineral’ incubations. Mineral transformations occurred under the influence of the soil porewater only and were primarily followed by X-ray diffraction analysis. A parallel set of mesh bags contained soil with 57Fe-labelled jarosite enrichment (Fe enriched in soil by a factor of 1.3 but 57Fe enrichment factor of 12.5–13.6), which allowed jarosite transformation to occur in close association with the soil matrix. Mineral transformations in 57Fe-jarosite-enriched soil were followed using 57Fe Mössbauer spectroscopy. In laboratory mesocosms and in the field, jarosite transformed most quickly in topsoil, whereas jarosite underwent limited transformation in subsoils, especially in laboratory mesocosms where Fe reduction was slow. The chemical environment around the jarosite affected the outcome of the transformation processes. Crystalline Fe oxyhydroxides, such as goethite, dominated the products in mesh bags where jarosite was not mixed with soil, whereas short-range-ordered or non-mineral Fe phases, such as Fe(II) sorbed to mineral surfaces or complexed with organic ligands, were dominant transformation products of jarosite when mixed in soil. Furthermore, Al substitution in jarosite caused contrasting effects in mesh bags containing pure minerals or mineral-enriched soil. Aluminium substitution slowed the transformation of jarosite in pure mineral mesh bags, but Al-substituted and unsubstituted jarosite showed similar transformation rates and pathways when incubated as a mixture with soil. The contrasting rate of transformation in topsoil and subsoil, the contrasting products of transformation in pure mineral mesh bags and 57Fe-jarosite-enriched soil, and the contrasting effect of Al substitution in pure mesh bags or jarosite-enriched soil, all demonstrate that the rate and products of jarosite transformation are defined by a balance between competitive transformation pathways that affect the transforming minerals.

Tailoring the lattice thermal conductivity of Al‐incorporated Ag2Se for near room temperature waste heat recovery

Ag2Se is categorized as a typical 'phonon‐liquid‐electron‐crystal (PLEC)'material, exhibiting an extremely low [[EQUATION]] valueTop of FormBottom of Form. In this study, Al substituted Ag2Se samples were synthesized by mechanical alloying process followed by hot press densification technique. The Al substituted sample shows an exceptionally high mobility of 2360 cm2V‐1S‐1 at room temperature and a maximum power factor of 1442 µWm‐1K‐2 at 383 K. The phonon scattering induced by various crystal imperfections due to Al substitution helped to obtain a very low lattice thermal conductivity [[EQUATION]] value of 0.328 W/mK. A high figure of merit (zT) of 0.4 at 383 K was obtained as a result of the simultaneous effect of boosting the electrical transport properties and decreasing the thermal conductivity. This present work summarizes that the Al substitution is highly significant in improving the thermoelectric properties of Ag2Se.

NiAlFe catalysts based on hydrotalcite-like precursors for low temperature CO2 methanation: Electronic effects among components and intrinsic activity of Ni site

NiAlFe catalysts based on the hydrotalcite-like precursor were prepared and the catalysts exhibit excellent low temperature catalytic activity for CO2 methanation. CO2 conversion over the NiAlFe0.3 catalyst is nearly 80 % under the condition of T = 225 °C, P = 1 atm, and WHSV = 24000 mL/(g∙h). With the increase in the substitution of Fe for Al, the hydrotalcite-like structure of the catalyst precursor is gradually destroyed; the reducibility of NiO component is promoted; the amount of surface basic site decreases. There is a strong electronic push–pull effect between NiO and Al2O3 in the calcined catalyst, and the electronic effect is weakened with the introduction of Fe because Fe3+ shares the responsibility of Ni2+ for donating electron to Al3+. In the reduced catalysts, the Ni3Fe alloy was formed and the electrons are pushed from Ni0 to Fe0. With the increase in the Fe amount, the number of surface Ni atom decreases, while the intrinsic activity of Ni active site enhances. The number and intrinsic activity of Ni site are the main two factors determining the CO2 methanation activity at low temperature. Moreover, the substitution of Al3+ by Fe3+ is beneficial for the stability of the catalysts by inhibiting the agglomeration of catalyst particle.

Effect of Al Substitution on Visible Short-Wave Infrared Reflectance Spectroscopy (VSWIR) of Goethite and Ferrihydrite

Goethite and ferrihydrite are the two major iron hydroxides, essential mineral constituents in the terrestrial surface system. Aluminum (Al) is the most common substituent in iron hydroxides, and it may significantly change the bulk and surficial physicochemical properties of iron hydroxides. Consequently, a practical and convenient approach is needed to efficiently identify the Al substitution degrees of iron hydroxides in natural occurrences. This study presents a comprehensive investigation of the VSWIR characteristics of laboratory-synthesized Al-substituted goethite and ferrihydrite, to establish diagnostic VSWIR parameters for the identification and quantification of Al substitution levels in iron hydroxides. The findings revealed that Al substitution can affect the band positions (P) of goethite and ferrihydrite at ~650 nm, ~900 nm, and ~1400 nm. The relationships between the Al substitution of ferrihydrite and VSWIR parameters can be expressed as P900 = −0.43 × Al(%) + 931 and P1400 = −0.07 × Al(%) + 1428, while that of goethite can be expressed as P650 = 0.42 × Al(%) + 657 and P900 = 2.29 × Al(%) + 936. The peak fitting results showed that the absorption intensity at 480–550 nm linearly decreases with increased Al substitution. The obtained VSWIR spectra of Al-substituted goethite and ferrihydrite provide a critical supplement to the spectral library for (Al) iron hydroxides, and these VSWIR parameters can be utilized for the semi-quantitative determination of Al substitution in natural iron hydroxides

Aluminum substitution stabilizes organic matter in ferrihydrite transforming into hematite: A molecular analysis

The association of soil organic matter (SOM) with iron (Fe) oxyhydroxides, particularly ferrihydrite, plays a pivotal role in the biogeochemical cycling of carbon (C) in both terrestrial and aquatic environment. The aging of ferrihydrite to more crystalline phases can impact the stability of associated organic C, a process potentially influenced by aluminum (Al) substitution due to its abundance. However, the molecular mechanisms governing the temporal and spatial distribution of SOM during the aging process of Al-substituted Fe oxyhydroxides remain unclear. This study aims to bridge this knowledge gap through a comprehensive approach, utilizing batch experiments, solid characterization techniques, and atomic force microscopy (AFM) based peak-force quantitative nanomechanical mapping (PF-QNM). Batch experiments revealed that humic acid (HA) was released into the aqueous phase during aging, with Al inhibiting this release. Various solid characterization methods collectively suggested that Al hindered the crystalline transformation of ferrihydrite and significantly preserved HA on the surface of newly formed hematite, rather than it being occluded within the interior of the new minerals. Results from 3-Dimensional fluorescence spectroscopy (3D-EEM) and Fourier-transform infrared spectroscopy (FTIR) indicated that the structure of HA remained constant, with the carboxyl-rich and hydroxyl-rich portions of HA fixed at the mineral interface during the aging period. Furthermore, we developed AFM-based PF-QNM to both quantify and visualize the interactions between Fe oxyhydroxides and HA, demonstrating variations in HA affinity among different Fe oxyhydroxides and highlighting the influence of the Al substitution rate.

Enhancement the electrical and linear/nonlinear optical properties of ZnCo2O4 through Al3+doping

In this work, ZnCo2O4 samples doped with Al3+ were prepared by the hydrothermal method. Synchrotron x-ray diffraction, FTIR, SEM and EDX techniques were used to investigate the structure, microstructure, morphology, and composition of ZnCo2-xAlxO4 samples. Rietveld analysis revealed a nearly inverse structure for the undoped ZnCo2O4. The degree of inversion is increased upon increasing the Al3+ doping content. Al ions preferentially occupy the octahedral B-site. The optical band gaps of ZnCo2−xAlxO4 samples are 1.9, 1.8 and 1.91 eV for x = 0, 0.1 and 0.2, respectively. Different empirical models were used to obtain the refractive index of the different samples using their corresponding optical band gaps. The increase in non-linear optical values in the sample with x = 0.1 suggested that this sample could be used in a variety of photonic applications. The effects of frequency and temperature on the dielectric permittivity, impedance and electrical modulus of different samples were explored. All samples exhibited the non-Debye relaxation phenomenon. The relaxation time of each sample is affected with the frequency and temperature. The Cole-Cole curve is employed to reduce uncertainty regarding the electrical characteristics of these ZnCo2−xAlxO4 samples induced by grain boundaries or bulk grain. The substitution of Al3+ ions can regulate the conductivity of the ZnCo2O4 sample.

Phase composition, crystal structures and enhanced microwave dielectric properties of Mg2+/Zr4+ co-doped Al2Mo3O12 ceramics

In this work, the substitution of Al3+ by Zr/Mg in Al2Mo3O12 was designed to enhance the quality factor while simultaneously adjusting the thermal stability of the resonant frequency. The Al2–2x(Zr0.5Mg0.5)2xMo3O12 (AMZM) (0.1 ≤ x ≤ 0.5) ceramics were synthesized using a simple solid-state method, resulting in all components exhibiting single-phase crystallinity and a dense structure. A phase transition temperature below room temperature was observed when x ≥ 0.4. Furthermore, the quality factor of the synthesized samples, compared to pure-phase Al2Mo3O12 (εr = 6.79, Q×f = 28471 GHz, τf = −48.77 ppm/℃), increased by nearly threefold. A detailed investigation of the crystal structure of the samples was conducted through Rietveld refinement. The composition with x = 0.3 (monoclinic phase) exhibited optimal dielectric performance after sintering at 800 ℃ for 6 h: εr = 7.84, Q×f = 86511 GHz, τf = −42.08 ppm/℃. By forming a composite ceramic with (Li1/2Sm1/2)MoO4, the negative τf value was further adjusted to near zero.

Rational design of an optimal Al-substituted layered oxide cathode for Na-ion batteries

Layered oxide cathodes, a promising avenue for Na-ion batteries, hold the highest potential for commercialization. Herein, we delve into the structural and electrochemical properties of Al-substituted layered oxides in our quest to pinpoint the optimal cathode composition in the Na3/4(Mn-Al-Ni)O2 pseudo-ternary system. The cathode materials investigated were synthesized in three distinct phase configurations, which include two monophasic configurations with P3 and P2-type structures and a third biphasic cathode with equal proportions of P3 and P2 phases. The fractions of the P3 and P2 type phases in the cathode materials were manipulated by adjusting the calcination temperature. The varying concentration of Mn3+ and Mn4+, confirmed by X-ray photoelectron spectroscopy, was found to impact the cyclic stability of these materials significantly. During electrochemical testing, the P3 cathodes showed impressive rate performance and exhibited an excellent specific capacity of 195 mAh g−1 at 0.1C. Regarding cyclic performance, the biphasic cathodes consistently outperformed their monophasic counterparts, with P3/P2-Na0.75Mn0.50Ni0.25Al0.25O2 exhibiting 82 % capacity retention after 300 cycles. Analysis of operando Synchrotron XRD data revealed an absence of P3 to O3 type phase transition in the cathodes even at low voltages where large structural variations to the unit cell structure were observed. The absence of P3 to O3 transformations and the superior electrochemical performance of Na0.75Mn0.50Ni0.25Al0.25O2 underlines the importance of Al substitution and P3/P2 biphasic structure in enhancing the electrochemical performance of layered oxides.

Investigation on the hydrocarbon adsorption performance enhancement of the ZSM-5 zeolite with different Si/Al ratio in the cold start process of the gasoline engine

In response to the issue of hydrocarbon emissions during the cold start process of gasoline engines, a hydrocarbon catcher coated with ZSM-5 zeolite was manufactured. The post-treatment system of the prototype vehicle was modified to install the hydrocarbon catcher, and cold start experiments on the vehicle under World Light-vehicle Test Cycle (WLTC) conditions were conducted. The experimental results showed that the hydrocarbon emissions in the low-speed stage of WLTC were much higher than those in other stages. In the early stages of cold start, the hydrocarbon catcher can reduce hydrocarbon emissions by up to 61 %. The analysis results of engine emissions showed that the content of various hydrocarbon components during cold start was: 60.1 % butene, 13.6 % acetylene, 11.3 % propylene, 7.3 % ethylene, 7.1 % acetaldehyde, and 0.6 % other components. Further molecular simulation studies were conducted on zeolite of different types and Si/Al ratios. The results showed that the adsorption of hydrocarbons on pure Si-MFI and -FER zeolites were less affected by H2O and CO2, making them ideal hydrocarbon capture materials. Al substitution introduced compensating cations into zeolite, which increased the adsorption capacity of H2O, CO2, and C2H4O with polar functional groups. Reducing the degree of Si/Al substitution is beneficial for hydrocarbon adsorption.

Pt-O-Ce interaction enhanced by Al substitution to promote the acetone degradation through accelerating the breaking of C[sbnd]C bond in acetic acid intermediate

The reaction rate of volatile organic compounds (VOCs) oxidation is controlled by the rate-limiting step in the total reaction process. This study proposes a novel strategy, by which the rate-limiting step of acetone oxidation is accelerated by enhanced chemical bond interaction with more electrons transfer through Al-substituted CeO2 loaded Pt (Pt/Al-CeO2). Results indicate that the rate-limiting step in the process of acetone oxidation is the decomposition of acetic acid. Al substitution enhances the Pt-O-Ce interaction that transfers more electrons from Pt/Al-CeO2 to acetic acid, promoting the breaking of its CC bond with a lower free energy barrier. Attributing to these, the reaction rate of Pt/Al-CeO2 is 13 times as high as that of Pt/CeO2 and its TOFPt value is 11 times as high as that of Pt/CeO2 at 150 °C. Moreover, the CO2 selectivity of Pt/Al-CeO2 also increases by 22 %. This work establishes the relationship between Pt-O-Ce interaction and acetone oxidation that provides novel perspectives on the development of efficient materials for VOCs oxidation.

Growth-associated emergence of spontaneous magnetization in Al-doped Cr2O3 thin film

Development of antiferromagnetic/ferrimagnetic materials has been an area of active pursuit to advance the antiferromagnetic/ferrimagnetic spintronics. In this paper, we investigated the emergence of the spontaneous magnetization MS in the antiferromagnetic Cr2O3 thin film by the Al substitution. In the case of the (Cr1-xAlx)2O3(0001) thin films, MS increases with increasing Al composition x up to x ∼0.21. The magnitude of MS decreases abruptly for x > 0.22, accompanied with the collapse of the crystal formation. We found that the induction of the spontaneous magnetization was highly associated with the growth process. The magnitude of MS depends on the growth direction of the film: MS at 10 K for x = 0.13±0.01 is 80 kA/m, 30 kA/m and 0 kA/m for (0001), (011¯2) and (112¯0) films, respectively. The difference in MS with the growth direction is relevant to the magnetic sublattice selective substitution of Al during the thin film growth. This specific substitution occurs in the growth plane having the layer-by-layer stacking of the magnetic sublattice, which was verified by the direct observations using the scanning transmission electron microscope.

Interaction between water and point defects inside volume-constrained α-quartz: An ab initio molecular dynamics study at 300 K

Quartz-based minerals in earth’s crust are well-known to contain water-related defects within their volume-constrained lattice, and they are responsible for strength-loss. Experimental observations of natural α-quartz indicate that such defects appear as hydroxyl groups attached to Si atoms, called Griggs defect (Si-OH), and molecular water (H2O) located at the interstitial sites. However, factors contributing to the formation of Griggs and interstitial H2O defects remain unclear. For example, the role of point defects like vacancy sites (O2− and Si4+), and substitutional (Al3+) and interstitial (Li+, K+, Ca2+, Mg2+, etc.) ions has remained largely unexplored. Here, we performed ab initio molecular dynamics at 300 K to examine the energetics and structure of water-related defects in volume-constrained α-quartz. Several configurations were systematically interrogated by incorporating interstitial H2O, O2− and Si4+ vacancies, substitutional Al3+, and interstitial Li+, Ca2+ and Mg2+ ions within α-quartz. Interstitial H2O defect was found to be energetically favorable in the presence of Substitutional Al3+, and interstitial Ca2+, Mg2+, and Li1+. In the presence of O2− and Si4+ vacancies, H2O showed a strong tendency to dissociate into OH—to form Griggs defect—and a proton; even in the presence of substitutional and interstitial ions. These ions distorted the α-quartz lattice and, in the extreme case, disrupted long-range order to form local amorphous domains; consistent with experimental reports. Our study provides an initial framework for understanding the impact of water within the crystal lattice of an anhydrous silicate mineral such as quartz. We provide not only thermodynamic and process-related information on observed defects, but also provides guidelines for future studies of water’s impact on the behavior of silicate minerals.

Effect of Al substitution on the magnetic, optical and electronic properties of KBiFe2O5 brownmillerite

We reveal the influence of non-magnetic Al3+ ion on magnetic, optical and electronic properties of KBiFe2O5. Al doped KBiFe2-xAlxO5 (x = 0, 0.2, 0.4) are synthesized by citrate combustion method. All the samples are found to be crystalized in monoclinic structure with P2/c space group. With Al doping, the grain size of the samples is reduced however, Fe ions maintain its +3 state. A mere difference in the low temperature zero field cooling and field cooling curve discards the multiple magnetic phases at low temperature, however, with Al, an improved magnetic moment is detected in the magnetic isotherms. A schematic model is adopted to explain the enhanced magnetization. Furthermore, the magnetic anomaly around the dielectric transition (760–780 K) depicts an existence of magnetoelectric coupling in all the samples. The optical band gap is reduced from 1.73 eV to 1.69 eV with Al doping. Extensive dielectric and electric modulus analysis is carried out to explore the conduction as well as relaxation process in the parent and Al doped system. The activation energy estimated from the electric modulus is (0.412 ± 0.021) eV for x = 0 and (0.370 ± 0.025) eV for x = 0.2 respectively but surprisingly, Al doping with x = 0.4 shows a completely different relaxation mechanism. Moreover, the frequency dependent ac conductivity is also explained and agrees well with the electric modulus data.