Physico-chemical characterization and possible uses of sludge processed from an urban sewage treatment plant.

Nowadays, the challenge is to transform dehydrated sewage sludge resulting from wastewater treatment plants from waste into resource. Following this objective, the sludge was further dried and submitted to X-ray diffraction (XRD) and FTIR analysis. The sludge was first dried in ventilated and unventilated spaces at 50 ∘C and 100 ∘C, for 60 and 100 minutes (min) in each case. The final mass and evaporation degree of the sludge depends on the initial mass, ventilation type, drying time, and temperature. The ventilated drying space is preferred for temperature control, homogeneity, and higher evaporation degree. The influence of the drying process on the structure and behavior of the sewage sludge was emphasized through X-ray diffraction (XRD) and FTIR analysis. The XRD shows good structural properties of the sludge samples given by the reduction of the particle size through evaporation. According to FTIR, evaporation influences the depolymerization of the silicate network. The hydroxyl units and metallic ion modifiers can improve the sludge structure, but its intensity decreases through evaporation. With high content of solid substance, and good relation between the composition of the sludge and its structure and behavior, the dried sewage sludge can be used in: (i) agriculture, (ii) construction, (iii) the energy sector.

Nanocomposites Derived from Construction and Demolition Waste for Cement: X-ray Diffraction, Spectroscopic and Mechanical Investigations.

In the production of cement, raw materials can be partially substituted by regenerable waste provided from glasses, construction and demolition waste in order to reduce the environmental problem and burden of landfills. In this study, limestone-silicate composites were synthesized using starting materials such as glass waste and lime, brick, autoclaved aerated concrete (ACC), mortar or plaster waste. The structure and mechanical properties of the nano-composite materials have been studied. The mean CaCO3 crystallite sizes are higher for composites containing ACC and brick than for doping with lime, mortar and plaster. Cement-based materials are formed by replacing 2.5% of the Portland cement with limestone-silicate composites. The results indicate new possibilities for introducing 2.5%of composites in cement paste because they promote the formation of the C-S-H network, which provides strength and long stability for the cement paste. The influence of varied types of mix composites in the expired cement on the initial cracking strain and stress, tensile strength and compressive strength were investigated. The compressive strength values of composite-expired cement specimens are situated between 11.8 and 15.7 MPa, respectively, which reflect an increase from 22.9 up to 63.54% over the compressive strength of expired cement matrix.

Development of Iron-Silicate Composites by Waste Glass and Iron or Steel Powders.

There is growing interest in the opportunities regarding construction and demolition wastes, such as glass and metal powders, for developing a circular economy and their transformation into new materials. This management and recycling of construction and demolition waste offers environmental benefits and conservation of natural resources. In this paper, new magnetic composite materials were prepared by wet chemical synthesis methods using crushed glasses and iron and steel waste powders as raw materials. The prepared iron-silicate composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, infrared (IR), ultraviolet-visible, and electron paramagnetic resonance (EPR) spectroscopy, and magnetic measurements. The XRD data confirm the formation of varied crystalline phases of the iron ions. The presence of the Fe3O4 crystalline phase was detected in the composites containing the iron waste powders. The inspection of the SEM micrographs revealed slightly better homogeneity for the composite material containing larger amounts of iron waste and heterogeneous morphology with cracks and random crystallinity for the composite doped with steel waste. By doping with different contents of iron or steel waste powder, structural modifications in the silicate network and the formation of new bands in the IR spectra were evidenced. The UV-Vis spectra were characterized by the absorption peaks for both the tetrahedral and octahedral geometries of the Fe3+ ions and the octahedral coordination of the Fe2+ ions with oxygen anions. The EPR data show resonance lines with g ~2, 4.3, and 6.4, corresponding to the Fe3+ ions. Using hysteresis curves, the superparamagnetic properties of the iron-silicate composites were evidenced.

Recycled and Nickel- or Cobalt-Doped Lead Materials from Lead Acid Battery: Voltammetric and Spectroscopic Studies.

The active mass of the plates of aspent car battery with higher wear after an efficient desulfatization can be used as sources of a new electrode. This paper proposes the recycling of spent electrodes from a lead acid battery and the incorporation of NiO or Co3O4 contents by the melt-quenching method in order to enrich the electrochemical properties. The analysis of X-ray diffractograms indicates the gradual decrease in the sulfated crystalline phases, respectively, 4PbO·PbSO4 and PbO·PbSO4 phases, until their disappearance for higher dopant concentrations. Infrared (IR) spectra show a decreasing trend in the intensity of the bands corresponding to the sulfate ions and a conversion of [PbO3] pyramidal units into [PbO4] tetrahedral units by doping with high dopant levels, yielding to the apparition of the PbO2 crystalline phase. The observed electron paramagnetic resonance (EPR) spectra confirm three signals located on the gyromagnetic factor, g~2, 2.2 and 8 assigned to the nickel ions in higher oxidation states as well as the metallic nickel nanoparticles. This compositional evolution can be explained by considering a process of the drastic reduction in nickel ions from the superior oxidation states to metallic nickel. The linewidth and the intensity of the resonance lines situated at about g~2, 2.17, 4.22 and 7.8 are attributed to the Co+2 ions from the EPR data. The best reversibility of the cyclic voltammograms was highlighted for the samples with x = 10 mol% of NiO and 15 mol% of Co3O4, which are recommended as suitable in applications as new electrodes for the lead acid battery.

Natrium Diacid Phosphate-Manganese-Lead Vitroceramics Obtained from Spent Electrodes.

NaH2PO4-MnO2-PbO2-Pb vitroceramics were studied usinginfrared (IR), ultraviolet-visible (UV-Vis) and electron paramagnetic resonance (EPR) spectroscopies to understand the structural modifications as potential candidates for electrode materials. The electrochemical performances of the NaH2PO4-MnO2-PbO2-Pb materials were investigated through measurements of cyclic voltammetry. Analysis of the results indicates that doping with a suitable content of MnO2 and NaH2PO4 removes hydrogen evolution reactions and produces a partial desulphatization of the anodic and cathodic plates of the spent lead acid battery.

Nanocomposites as Substituent of Cement: Structure and Mechanical Properties.

To date, the scientific research in the field of recycling of construction and demolition wastes was focused on the production of concrete, cements, and bricks. The attainment of these products was limited to the addition of suitable binder contents, such as lime or cement, compaction, and possibly heat treatment, without a concrete recycling method. In this paper, new cement materials consisting of 2.5 weight% composite and originating from construction and demolition waste powder, were prepared and investigated in view of applications in the construction industry as a substituent of cement. The materials with recycled powder from construction and demolition wastes were characterized by X-ray diffraction (XRD), infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. The XRD data indicate vitroceramic structures with varied crystalline phases. The NMR relaxometry data show four reservoirs of water associated with bounded water and with three types of pores in the composite construction material. The micro-Vickers hardness was measured to reflect the influence of composite nature in the local mechanical properties of the composite-cement for the mixture with Portland cement and (EC) expired cement.

Structural, Optical, and Magnetic Studies of the Metallic Lead Effect on MnO2-Pb-PbO2 Vitroceramics.

MnO2-lead materials have attracted attention in their applications as electrodes. This work reports a detailed spectroscopic study of the compositional variation of MnO2-xLead vitroceramic materials with varied Pb contents. The concentration variation of lead and manganese ions issystematically characterized throughthe analysis of X-ray diffraction (XRD), Fourier transform infrared (FTIR), ultraviolet-visible (UV-Vis), and electron paramagnetic resonance (EPR) spectroscopy.The MnO2-xLead samples consist of a vitroceramic structure with Pb, PbO, PbO2,and Mn3O4 crystalline phases. The introduction of higher Pb content in the host vitroceramic reveals the [PbO6]→[PbOn] conversion, where n = 3, 4, and the formation of distorted [MnO6] octahedral units. The UV-Vis data of the samples possess the intense bands between 300 and 500 nm, which are due to the presence of divalent lead ions (320 nm) and divalent and trivalent manganese ions (420 and 490 nm, respectively) in the structure of glass ceramics. The EPR data show resonance lines located around g ~ 8 and 4.3, and a sextet hyperfine structure at g ~ 2, which isascribed to the Mn+3 and Mn+2 ions.

Experimental and theoretical investigations on the structure-properties interrelationship of the gadolinium-vanadate-germanate glasses.

Glasses in the system xGd2O3·(100-x)[GeO2·V2O5] with 0 ≤ x ≤ 20 mol% have been prepared from the melt quenching method. In this paper, we investigated changes in germanium coordination number in gadolinium-vanadate-germanate glasses through molar volume analysis, measurements of densities, investigations of FTIR and UV-VIS spectroscopy, calculations of density functional theory (DFT). Analyzing the structural changes resulted from the IR spectra we found that the gadolinium ions have a pronounced affinity toward [VO4] structural units which contain non-bridging oxygens necessary for the charge compensation. The introduction of the excess of oxygen yields the formation of [VO5] structural units. This attains maximum value at 5 mol% Gd2O3, in agreement with the density measurements. Further, the addition of the surplus of oxygen implies the transformation of [VO5] to [VO4] structural units and the formation of VO4⁻³ orthovanadate structural units. The UV-VIS spectra show a broad UV absorption band located in the 300-500 nm region. These bands are assumed to originate from the combination of vanadium ions possibly present in the three states of valence. The presence of Ge-Ge wrong bonds attains its maximum values in the samples with x = 5 and 15 mol% Gd2O3 (bands centered in the 250-300 nm range). DFT calculations show the massive vibrations of the [VO(n)] structural units coupled with each other via [GeO6] and [GeO4] structural units. This leads to the splitting of the bridge modes and a multiplication of the number of these bands.

FTIR, Raman, and UV-Vis spectroscopic and DFT investigations of the structure of iron-lead-tellurate glasses.

In this work, the effects of iron ion intercalations on lead-tellurate glasses were investigated via FTIR, Raman and UV-Vis spectroscopies. This homogeneous glass system has compositions xFe(2)O(3)·(100-x)[4TeO(2)·PbO(2)], where x = 0-60 mol%. The presented observations in these mechanisms show that the lead ions have a pronounced affinity towards [TeO(3)] structural units, resulting in the deformation of the Te-O-Te linkages, and leading to the intercalation of [PbO( n )] (n = 3, 4) and [FeO( n )] (n = 4, 6) entities in the [TeO(4)] chain network. The formation of negatively charged [FeO(4)](1-) structural units implies the attraction of Pb(2+) ions in order to compensate for this electrical charge. Upon increasing the Fe(2)O(3) content to 60 mol%, the network can accommodate an excess of oxygen through the formation of [FeO(6)] structural units and the conversion of [TeO(4)] into [TeO(3)] structural units. For even higher Fe(2)O(3) contents, Raman spectra indicate a greater degree of depolymerization of the vitreous network than FTIR spectra do. The bands due to the Pb-O bond vibrations are very strongly polarized and the [TeO(4)] structural units convert into [TeO(3)] units via an intermediate coordination stage termed "[TeO(3+1)]" structural units. Our UV-Vis spectroscopic data show two mechanisms: (i) the conversion of the Fe(3+) to Fe(2+) at the same time as the oxidation of Pb(2+) to Pb(+4) ions for samples with low Fe(2)O(3) contents; (ii) when the Fe(2)O(3) content is high (x ≥ 50 mol%), the Fe(2+) ions capture positive holes and are transferred to Fe(3+) ions through a photochemical reaction, while the Pb(2+) ions are formed by the reduction of Pb(4+) ions. DFT calculations show that the addition of Fe(2)O(3) to lead-tellurate glasses seems to break the axial Te-O bonds, and the [TeO(4)] structural units are gradually transformed into [TeO(3+1)]- and [TeO(3)]-type polyhedra. Analyzing these data further indicates a gradual conversion of the lead ions from covalent to ionic environment. There is then a charge transfer between the tri- and tetracoordinated tellurium atoms due to the capacity of the lead-tellurate network to form the appropriate coordination environments containing structural units of opposite charge, such as iron ions, [FeO(4)](1-).

Experimental and theoretical studies of the structure of tellurate-borate glasses network.

The structural properties of the xTeO(2) x (1-x)B(2)O(3) glasses (x = 0.6; 0.7) were investigated by FT-IR spectroscopy. From the analysis of the FTIR spectra, it is reasonable to assume that by the increasing of boron ions content, the tetrahedral [BO(4)] units are gradually replaced by the trigonal [BO(3)] units. The increase in the number of non-bridging oxygen atoms would decrease the connectivity of the glass network and will yield the depolymerization of the borate chains. The molecular structure and vibrational frequencies of the proposed structural models have been studied by exploring the density functional theory (DFT) calculations. The FTIR spectra of the xTeO(2) x (1-x)B(2)O(3) vitreous systems were compared with the calculated spectrum. This procedure allowed us to assign most of the observed IR bands.