M. Amjoud

Lead-free Ba0.8Ca0.2(ZrxTi1−x)O3 ceramics with large electrocaloric effect

The electrocaloric effect was investigated in lead-free Zr doped Ba0.8Ca0.2(ZrxTi1−x)O3 (BCTZ) ceramics synthesized by a conventional sintering process. Room-temperature x-ray diffraction analysis showed that the tetragonal structure is obtained in BCTZ for x  ≤ 0.08 and a pseudo cubic phase for x > 0.08. The dielectric spectroscopy and calorimetry revealed that the Curie temperature decreases as a consequence of Zr doping and that the BCTZ exhibits a first order ferroelectric phase transition. The electrocaloric effect was determined by the calculation of the electrocaloric change of temperature (ΔT) using the Maxwell relation based on the P–E hysteresis loops measured at different temperatures. A large electrocaloric responsivity ΔT/ΔE = 0.34 × 10−6 Km/V was found for x = 0.04, which significantly exceeds of values found so far in other lead-free electrocaloric materials.

Elucidating the crystal-chemistry of Jbel Rhassoul stevensite (Morocco) by advanced analytical techniques

Abstract The composition of Rhassoul clay is controversial regarding the nature of the puremineral clay fraction which is claimed to be stevensite rather than saponite. In this study, the raw and mineral fractions were characterized using various techniques including Fourier transform infrared spectroscopy and magic angle spinning nuclear magnetic resonance (MAS NMR). The isolated fine clay mineral fraction contained a larger amount of Al (>1 wt.%) than that reported for other stevensite occurrences. The 27Al MAS NMR technique confirmed that the mineral is stevensite in which the Al is equally split between the tetrahedral and octahedral coordination sites. The 29Si NMR spectrum showed a single unresolved resonance indicating little or no short-range ordering of silicon. The chemical composition of the stevensite from Jbel Rhassoul was determined to be ((Na0.25K0.20)(Mg5.04Al0.37Fe0.20⃞0.21)5.61(Si7.76Al0.24)8O20(OH)4). This formula differs from previous compositions described from this locality and shows it to be an Al-bearing lacustrine clay mineral.

MINERALOGICAL AND PHYSICO-CHEMICAL CHARACTERIZATIONS OF FERRUGINOUS BEIDELLITE-RICH CLAY FROM AGADIR BASIN (MOROCCO)

The mechanism of formation of detrital, beidellite-rich clay occurring in the Agadir basin (Morocco) is well documented, but its detailed characterization is incomplete which limits its application. The aim of the present study was to provide further details of the mineralogical and physico-chemical characteristics of this clay. Bulk raw clay and its Na+-saturated, <2 μm fraction were characterized using chemical, structural, and thermal techniques. Measurements of induced streaming potential (e.g. particle charge) and of specific surface area and porous volume are reported. The raw clay contained carbonate and quartz as associated minerals along with phyllosilicates (<2 μm particle size). X-ray diffraction and scanning electron microscopy analyses showed that the <2 μm fraction was dominated by a dioctahedral smectite. Because dehydroxylation of this mineral occurred at 510°C, and because it re-expanded in ethylene glycol after Li+-saturation followed by heating at 240°C for 24 h, the mineral was shown to be a beidellite rather than montmorillonite. This assertion was further supported by 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectra showing predominantly negative charges in the tetrahedral sheets due to notable Al-for-Si substitutions. The chemical composition of the <2 μm fraction showed an Fe2O3 content which was ~7.52 wt.% greater than those of other beidellite occurrences but not so much that it would be identified as a nontronite. The absence of stretching and bending absorption bands corresponding to characteristic (Fe2OH) units in mid-infrared spectra and their corresponding fundamental overtones or combination bands in near-infrared spectra supported this notion. The structural formula of the beidellite in the present study was determined to be (Si7.51Al0.49)(Al2.99Fe0.68Mg0.33) (Ca0.03Na0.54Mg0.11)O20(OH)4, having dioctahedral ferruginous characteristics with almost 60% of the negative charge found in tetrahedral sheets. The cation exchange capacity determined from the structural formula was ~108 meq/100 g. The specific surface area and total pore volume were ~82.2 m2/g and 0.136 cm3/g, respectively. Interestingly, a detrital rather than a hydrothermal-alteration origin, as reported for other beidellite occurrences, explains its natural abundance and emphasizes the great interest in it.

Electrocaloric effect in Ba0.2Ca0.8Ti0.95Ge0.05O3 determined by a new pyroelectric method

The present letter explores the electrocaloric effect (ECE) in the lead-free oxide Ba 0.8 Ca 0.2 Ti 0.95 Ge 0.05 O 3 ceramics (BCTG). The electrocaloric responsivity was determined by two different methods using the Maxwell relationship . In a first well-known indirect method, hysteresis loops were measured in a wide temperature range from which the pyroelectric coefficient and thus ξ were determined by derivation of data. In the second novel method the pyroelectric coefficient p E and consequently the electrocaloric responsivity ξ were determined by direct measurements of the pyroelectric currents under different applied electric fields. Within the experimental error, good agreement was obtained between two methods with at about 410 K.

Lead free Ba0.8Ca0.2TexTi1−xO3 ferroelectric ceramics exhibiting high electrocaloric properties

Direct and indirect electrocaloric measurements were performed on the new Tellurium (Te) doped Ba0.8Ca0.2TiO3 (BCT) ceramics. The effects of Te addition on structural, electrical, and electrocaloric properties of BCT ceramics were investigated. The incorporation of the Te element in the BCT induced the decrease of the Curie temperature and the enhancement of the electrocaloric effect. The significant electrocaloric temperature change ΔT = 1.237 K determined by the direct method was obtained at the relatively moderate field of ∼25 kV/cm in Ba0.8Ca0.2Ti(1−x)TexO3 with x = 0.02. The corresponding electrocaloric responsivity ΔT/ΔE = 0.495 × 10−6 K m V−1 is higher than that observed in pure BCT ceramics and is one of the highest reported so far in lead-free ferroelectric materials. The materials coefficient of performance was determined at the phase transition with a maximal value of 14.7.

Impedance spectroscopy studies on lead free Ba 1-x Mg x (Ti 0.9 Zr 0.1 )O 3 ceramics

Abstract Ba1-xMgx(Ti0.9Zr0.1)O3 (x = 0.01 and 0.02) ceramics were prepared using the conventional solid state reaction. Rietveld refinement performed on X-ray diffraction patterns indicates that the samples are tetragonal crystal structure with P4mm space group. By increasing Mg content from 1 to 2% the unit cell volume decreased. Likewise, the grains size is greatly reduced from 10 μm to 4 μm. The temperature dependence of dielectric constants at different frequencies exhibited typical relaxor ferroelectric characteristic, with sensitive dependence in frequency and temperature for ac conductivity. The obtained activation energy values were correlated to the proposed conduction mechanisms.