Pulsed laser deposition of Mg–Al layered double hydroxide with Ag nanoparticles

Powdered layered double hydroxides (LDHs)—also known as hydrotalcite-like (HT)—compounds have been widely studied due to their applications as catalysts, anionic exchangers or host materials for inorganic or organic molecules. Assembling thin films of nano-sized LDHs onto flat solid substrates is an expanding area of research, with promising applications as sensors, corrosion-resistant coatings, components in optical and magnetic devices. The exploitation of LDHs as vehicles to carry dispersed metal nanoparticles onto a substrate is a new approach to obtain composite thin films with prospects for biomedical and optical applications. We report the deposition of thin films of Ag nanoparticles embedded in a Mg–Al layered double hydroxide matrix by pulsed laser deposition (PLD). The Ag-LDH powder was prepared by co-precipitation at supersaturation and pH = 10 using aqueous solutions of Mg and Al nitrates, Na hydroxide and carbonate, and AgNO₃, having atomic ratios of Mg/Al = 3 and Ag/Al = 0.55. The target to be used in laser ablation experiments was a dry pressed pellet obtained from the prepared Ag-LDH powder. Three different wavelengths of a Nd:YAG laser (266, 532 and 1064 nm) working at a repetition rate of 10 Hz were used. X-Ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and secondary ions mass spectrometry (SIMS) were used to investigate the structure, surface morphology and composition of the deposited films.     

Magnetic behavior of Mg–Al–Zn–Fe mixed oxides from precursors layered double hydroxide

Mixed oxides of Mg–Al–Zn–Fe were obtained by calcination of layered double hydroxides (LDH) prepared by coprecipitation reaction with hydrothermal treatment. The structural characterization of precursors and oxides was carried out by X rays diffraction, showing increases of ZnO phase with the increase of the zinc content. Magnetic behavior was studied by vibrating sample magnetometer (VSM) and by a superconducting quantum interference device (SQUID) showing both paramagnetic and super paramagnetic behavior depending on both particles size and composition.     

ESR spectra and thermal diffusivity of Zn–Al layered double hydroxide

Zn–Al–NO₃–LDH was synthesized using the co-precipitation method at pH 7±0.1 and ratio Zn/Al=4. The heat treatment of LDH was studied by X-ray diffraction (XRD) and thermogravimetric analysis (TGA/DTG) to investigate the stability of the LDH structure. The in situ electron spin resonance (ESR) spectra of fresh LDH from room temperature up to 190 °C were obtained, which are due to the presence of nitrate radicals in LDH interlayer. ESR spectra of sintered LDH below 200 °C (ex situ ESR spectra) were investigated, which are also due to the nitrate radicals. However, at 200 °C and above, spectra were due to the oxygen vacancies of ZnO, which was formed during the thermal treatment of LDH. Thermal diffusivity of LDH as a function of in situ temperatures results in a nonlinear relation, which is due to the changing water content of LDH when temperature increases. However, thermal diffusivity of LDH as a function of sintered temperatures showed a linear relation and the slope of these data demonstrated the dependency between thermal diffusivity and water content of LDH below 200 °C. For temperature above 180 °C, the thermal diffusivity behavior was mainly due to the ZnO phase in LDH.     

Adsorption properties of Mg–Al layered double hydroxides thin films grown by laser based techniques

Powdered layered double hydroxides (LDHs) have been widely studied due to their applications as catalysts, anionic exchangers or host materials for inorganic and/or organic molecules. Assembling nano-sized LDHs onto flat solid substrates forming thin films is an expanding area of research due to the prospects of novel applications as sensors, corrosion-resistant coatings, components in optical and magnetic devices.Continuous and adherent thin films were grown by laser techniques (pulsed laser deposition – PLD and matrix assisted pulsed laser evaporation – MAPLE) starting from targets of Mg–Al LDHs. The capacity of the grown thin films to retain a metal (Ni) from contaminated water has been also explored. The thin films were immersed in an Ni(NO₃)₂ aqueous solutions with Ni concentrations of 10^?3% (w/w) (1 g/L) and 10^?4% (w/w) (0.1 g/L), respectively. X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX) were the techniques used to characterize the prepared materials.     

Laser surface modification of Al–4Cu–1Mg alloy for enhanced thermal conductivity

The feasibility of enhancing thermal conductivity of Al–4Cu–1Mg alloy by depositing 80Cu–20Mo coating using high-power lasers has been examined. Coatings of 667±2.5 μm thickness were formed with metallurgically sound interface. Results showed an 86% increase in the thermal conductivity of Al–4Cu–1Mg alloy due to laser-deposited 80Cu–20Mo alloy coating. This coating approach can potentially be used on low coefficient of thermal expansion metal matrix composites to enhance their thermal conductivity in electronic devices.     

Estimation of the solubility product of hydrocalumite–hydroxide,a layered double hydroxide with the formula of [Ca2Al(OH)6]OH·nH2O

From aqueous NaOH/Ca(OH)₂/NaAl(OH)₄ mixtures, after allowing short reaction times we observed the precipitation of Ca(OH)₂(s) at lower, and a mixture of Ca(OH)₂(s) and a layered double hydroxide, hydrocalumite (HC) at higher aluminate concentrations. From the maximum aluminate concentration, at which the equilibrium solid phase is still portlandite (i.e., further increase in the aluminate concentration results in HC appearing in the precipitate beside the portlandite), the concentration based solubility products of two polymorphs of HC with the formula of [Ca₂Al(OH)₆]OH·nH₂O (differing in n) has been estimated and was found to be log L_HC=−11.4 at 25 °C and −12.1 at 75 °C, respectively (where L_HC=[Ca²⁺]²[Al(OH)₄⁻][OH⁻]³) and at constant ionic strength (I=1 M NaCl). To the best of our knowledge, this is the first published estimate for the solubility product of hydrocalumite. Additionally, from the composition obtained for NaOH/Ca(OH)₂/NaAl(OH)₄ mother liquors in equilibrium with Ca(OH)₂(s), attempts were made to extract the formation constant of the ion pair CaAl(OH)₄⁺. It was found, that the effects caused by the supposed formation of this solution species are too small to be reliably determined, which allowed an upper estimate for its formation constant, K, to be suggested in the temperature range of 25–75 °C (K<200 and 40 M⁻¹ at 25 and 75 °C, respectively).     

Utilization of Mg2Al–layered double hydroxide as an effective sequestrator to trap Cu(II) ions from aqueous solution impacted by water quality parameters

Recently, Mg₂Al–layered double hydroxide (Mg₂Al–LDH) has been extensively studied as promising candidates to trap metal ions due to their high complexation and adsorption capacity. Herein, Mg₂Al–LDH was utilized as an effectiveness sequestrator to trap Cu(II) ions from aqueous solution by an adsorption process using batch technique under ambient conditions. The results showed that Cu(II) adsorption on Mg₂Al–LDH increases with pH increasing and maintains a high level at pH>7.0. The adsorption of Cu(II) was obviously affected by ionic strength at low pH, which was not dependent on ionic strength at high pH. The presence of HA or FA promotes the adsorption of Cu(II) on Mg₂Al–LDH at low pH values, while reduces the adsorption of Cu(II) at high pH values. The adsorption isotherms of Cu(II) on Mg₂Al–LDH at three different temperatures were simulated by the Langmuir, Freundlich, and Dubinin-Radushkevitch (D–R) models very well. The thermodynamic parameters were determined from the temperature-dependent adsorption, and the results showed that Cu(II) adsorption on Mg₂Al–LDH was exothermic and the process was favored at high temperature. The results suggest that Mg₂Al–LDH is suitable as a sorbent material for the recovery and attenuation of Cu(II)-polluted wastewater.     

Controllable synthesis of layered Co–Ni hydroxide hierarchical structures for high-performance hybrid supercapacitors

A facile solvothermal method is developed for synthesizing layered Co–Ni hydroxide hierarchical structures by using hexamethylenetetramine (HMT) as alkaline reagent. The electrochemical measurements reveal that the specific capacitances of layered bimetallic (Co–Ni) hydroxides are generally superior to those of layered monometallic (Co, Ni) hydroxides. The as-prepared Co_0.5Ni_0.5 hydroxide hierarchical structures possesses the highest specific capacitance of 1767 F g⁻¹ at a galvanic current density of 1 A g⁻¹ and an outstanding specific capacitance retention of 87% after 1000 cycles. In comparison with the dispersed nanosheets of Co–Ni hydroxide, layered hydroxide hierarchical structures show much superior electrochemical performance. This study provides a promising method to construct hierarchical structures with controllable transition-metal compositions for enhancing the electrochemical performance in hybrid supercapacitors.     

Correlation of the properties of ionic conductivity–structure for the RbGaO2 solid electrolyte

Physics of the Solid State - The crystal structure of rubidium gallate RbGaO2 in the temperature range of 300–853 K has been investigated using high-temperature neutron diffraction. The...     

Synthesis and photochemical properties of zinc–aluminum layered double hydroxide/organic UV ray absorbing molecule/silica nanocomposites

Organic ultraviolet (UV) ray absorbents have been used as sunscreen materials, but may pose a safety problem when used at high concentration. In order to prevent direct contact of organic UV ray absorbent to the human skin several organic UV absorbents such as 4-hydroxy-3-methoxybenzoic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 4-hydroxy-3-methoxycinnamic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, p-aminobenzoic acid and urocanic acid were intercalated into Zn₂Al layered double hydroxides (Zn₂Al-LDHs) by anion-exchange and/or co-precipitation reaction. Thereafter, the obtained nanocomposites were coated with amorphous silica. Significant amounts (20–40 mass%) of organic UV absorbers were intercalated as univalent and/or divalent anions. The UV ray absorption ability of the organic UV absorbents increased and their catalytic activity for the air oxidation of castor oil greatly decreased when they were intercalated into the interlayer spaces of the Zn₂Al-LDHs. The deintercalation of organic molecules from LDHs by the anion exchange reaction with carbonate ion could be greatly depressed by coating the nanocomposite powder with amorphous silica.     

Characterization of organic–inorganic hybrid layered perovskite and intercalated compound (n-C12H25NH3)2ZnCl4

We report on some electrical properties and solid–solid phase transitions of organic–inorganic hybrid layered halide perovskite and intercalated compound (n-C₁₂H₂₅NH₃)₂ZnCl₄ which is one member of the long-chain compounds of the series (n-C_nH_2n+1NH₃)_2,(n = 8–18). The complex dielectric permittivity ?*(ω,T) and the ac conductivity σ (ω,T) were measured as functions of temperature 100 K < T < 390 K and frequency 5 kHz < f < 100 kHz. Moreover, the differential scanning calorimetery and the differential thermal analysis thermograms were performed. The analysis of our data confirms the existence of a structural phase transition at T ≈ (362?±?2) K, where the compound changes its state from intercalation to non-intercalation with a drastic increase in the c-axis by about 16.4%.

The behavior of the frequency-dependent conductivity follows the Jonscher universal power law: σ (ω, T) α?^s(?,T). The mechanism of electrical conduction in the low-temperature phase (phase II) can be described as quantum mechanical tunneling model.     

Enhancement of ionic conductivity in the composite solid electrolyte system: TlI–Al2O3

This paper reports the heterogeneously doped alumina (Al₂O₃) on the ionic conductivity of thallium iodide. Composite materials of formula (1 − x) TlI–xAl₂O₃, x = 0–0.7 have been prepared and studied by X-ray diffraction, differential scanning calorimetry, and electrical conductivity. X-ray diffraction and differential scanning calorimetry proved the formation of composite in this binary system. The maximum enhancement observed is about three orders of magnitude with respect to the host material. The enhancement of electrical conductivity in comparison with pure thallium iodide can be interpreted with the space charge layer model. Moreover, the increased content of alumina in the system leads to the disappearance of phase transition β–α thallium iodide, which is usually observed in the pure compound. This behavior was explained by stabilizing effect of β-phase at high temperatures and suppression of α-phase at higher contents of alumina.     

Organic–inorganic detectors with Al2O3:C microcrystallites

Optically stimulated luminescence (OSL) is a known phenomenon with several applications in various fields of radiation dosimetry. This phenomenon may be used for estimating dose of absorbed radiation as well as the age of archeological and geological samples. For some applications (e.g. in medicine) it would be develop detectors in the form of high-area flexible foils. This could be achieved by incorporating small grains of typical inorganic crystalline OSL phosphors into organic (polymer) matrix. In the present study we prepared samples containing Al₂O₃:C microcrystalline grains in polymeric matrices. Polymer matrices change the OSL readout and significantly influence the total OSL response. We observed that the dose responses of investigated hybrid materials are linear in the studied range and depend on the types of the matrix and radiation.     

Determination of the ionic conductivity of Sr-doped lanthanum manganite by modified Hebb–Wagner technique

The Hebb–Wagner polarization method with the electron blocking electrode has been discussed in this paper in aim to determine a partial ionic conductivity of Sr-doped lanthanum manganite. The “limiting current” in the proposed system was measured using the two-point DC technique with additional Pt electrode between LSM and blocking electrode. The electrochemical model based on bulk diffusion processes and Boltzmann statistics has been also described. The ionic conductivity calculated with the use of proposed model for La_0.7Sr_0.3MnO_3+δ was 5.3×10⁻⁴ S cm⁻¹ at 800 °C and the activation energy of ionic conductivity was found to be (0.60±0.02) eV. This result is in agreement with previous literature reports and indicates the workability of the modified Hebb–Wagner system.     

The effect of humidity on the ionic conductivity of Mg2+-stabilized K+-β-ferrite

The ionic conductivity of Mg²⁺-stabilized potassium β-ferrites was studied in wet and dry air atmosphere and in the temperature range between room temperature and 500 °C. Several conductivity processes were determined. The impedance spectroscopic measurements were combined with thermogravimetric analysis data, and a microscopic interpretation for the effect of humidity on the conductivity of K⁺-β-ferrite is proposed. Between 400 and 500 °C, a change in the conductivity behavior is observed which is associated with the magnetic ordering temperature and a structural ordering in the conductivity planes of the materials. The activation energy values of the different conduction processes have been calculated.     

Atomic-scale simulation of intergranular segregation of H in Al–Mg: implications for H-induced damage

The goal of this work is to make a contribution to the understanding of the microscopic mechanisms of H-induced intergranular damage. We develop an embedded-atom method interatomic potential for H in the Al–Mg system with the main aim of reproducing the current understanding of H trapping to vacancies. This model is used to investigate the effect of the Mg–H affinity on the segregation of H on the Σ =5 (310) [001] grain boundary. Monte Carlo simulations in the grand canonical ensemble are used to estimate equilibrium H concentrations at this boundary at T=300?K. A large structure change, associated with the H enrichment of the grain boundary, is reported. The implications on damage to the interface are discussed.     

Aberration-corrected HAADF-STEM investigations of precipitate structures in Al–Mg–Si alloys with low Cu additions

Precipitates in a lean Al–Mg–Si alloy with low Cu addition (~0.10 wt.%) were investigated by aberration-corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Most precipitates were found to be disordered on the generally ordered network of Si atomic columns which is common for the metastable precipitate structures. Fragments of known metastable precipitates in the Al–Mg–Si–(Cu) alloy system are found in the disordered precipitates. It was revealed that the disordered precipitates arise as a consequence of coexistence of the Si-network. Cu atomic columns are observed to either in-between the Si-network or replacing a Si-network column. In both cases, Cu is the center in a three-fold rotational symmetry on the Si-network. Parts of unit cells of Q′ phase were observed in the ends of a string-type precipitates known to extend along dislocation lines. It is suggested that the string-types form by a growth as extension of the B′/Q′ precipitates initially nucleated along dislocation lines. Alternating Mg and Si columns form a well-ordered interface structure in the disordered Q′ precipitate. It is identical to the interface of the Q′ parts in the string-type precipitate.