Sulfate Crystals Research Articles

Service of refractories in the regenerator nozzle glass furnace

The exhaust flue gases in glass furnaces include products of gas combustion and charge degassing, as well as products of evaporation from the glass melt. Of the main (CO2, H2O, N2 and O2) and secondary (Na, NaOH, Na2SO4, NaCl, HCl and SO2) smoke components for the service of refractories in the regenerator nozzle, sodium sulfate is the most problematic. The change in the aggregate state of gaseous Na2SO4 during the smoke cooling process gives rise to the release of two zones in the middle part of the nozzle: condensation and crystallization of sodium sulfate. Specifying the temperature intervals within which condensation (1100‒880 °C) and crystallization (880‒725 °C) of sodium sulfate occur allows us to formalize the technical conditions for the design of nozzles for single-turn and multi-turn regenerators of glass furnaces.

Lead-acid battery desulfation using a high-frequency pulse desulfator in standalone PV systems

The work presented in this article contributes to the study of a standalone photovoltaic (PV) system with battery storage by creating an electronic board that allows for the recovery of the battery's capacity using pulse technology that uses high-energy pulses from the PV panel to break down and remove the sulfation buildup, which is a contributing factor in the failure of most lead-acid batteries. Different methods or treatments can be used to lessen the impact of sulfation or even get rid of it and achieve battery rejuvenation. Battery sulfation is a process in which sulfate crystals form on the plates of a lead-acid battery, impeding its ability to retain a charge, and decreasing the battery’s overall effectiveness. This process can happen due to various reasons, such as charging for a shorter time than required, charging for a longer period of time than required, or even not charging it for quite some time. Sulfation affects a battery’s lifespan and comes with adverse effects on its performance, though it can be prevented.

High Strength Anhydrite Cement Based on Lime Mud From Water Treatment Process: One Step Synthesis in Water Environment, Characterization and Technological Parameters

ABSTRACTIn the process of water treatment from surface water sources, lime mud as waste is formed. This waste contains CaO, Ca(OH)2, and CaCO3. The article proposes a comprehensive method for processing lime mud into high‐strength anhydrite cement. The method involves the interaction of lime mud with waste sulfuric acid from the production of polymer fibers using a structure‐controlled method in the (CaO·Ca(OH)2·CaCO3)—H2SO4—H2O system at a temperature of 40°C. X‐ray diffraction analysis showed the presence of CaSO4 and CaSO4·0.62H2O phases with a purity of 99.8%. The structure‐controlled method makes it possible to control the formation and growth of calcium sulfate crystals of the required shape and size, due to which it is possible to obtain anhydrite cement with desired properties. Combined grinding of synthetic anhydrite with activator additives makes it possible to obtain anhydrite cement with a strength of up to 28.5 MPa.

Crystal Growth, Optical, Mechanical and Dielectric Analysis of Semiorganic Glycine Manganese Sulphate Single Crystal for Opto‐Electronic Device Application

AbstractGlycine manganese sulphate (GMS) crystals are produced by a slow evaporation technique at room temperature. This is confirmed that triclinic of the crystal lattice system by using single crystal X‐ray diffraction analysis and to determine the lattice parameters of the synthesised crystals. Powder XRD is used to confirm the planar indexing and crystalline structure. The Fourier Transform Infrared (FT‐IR) spectra are examined to verify that functional groups are present in the generated GMS crystals. By establishing a cut‐off wavelength of 253 nm, spectra of visible, near‐infrared, and Ultra Violet (UV) light from 200 to 1100 nm are analyzed. At frequencies ranging from 100 Hz to 8 MHz, the grown crystal's dielectric response is studied. Vickers microhardness tester is utilized to find out how strong the grown crystal is mechanically. Photoluminescence (PL) investigations often aim to detect crystal formation faults and contaminants. Etching analysis is used to find surface flaws and dislocations on the formed crystal's surface. The internal surface property of the produced crystal is investigated with scanning electron microscopy (SEM). The findings contradicted each other, suggesting that the created GMS crystal be used in opto‐electronic device applications.

A simple room-temperature refurbishment method for sulfated lead-acid batteries using ammonium acetate treatment

Current recycling paradigms of lead-acid batteries (LABs) involve the use of toxic, polluting, and energy-demanding processes. Here we report a novel strategy to refurbish LABs which failed due to the formation of hard sulfation on the anodes. We used ammonium acetate (NH4Ac) to selectively dissolve the water-insoluble lead sulfate (PbSO4) crystals which cause the hard sulfation from commercial LAB anodes and electrodeposit metallic lead on a new surface. The remarkable removal of hard sulfation was characterized by a combination of X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX). The treatment replenished a fresh LAB anode surface, recovering the capacity from ∼0 % to 99 %. The dissolved Pb2+ was retrieved with an efficiency of >99.9 % through electrodeposition, completing a refurbishing process that minimizes the release of heavy metals into the environment. We demonstrated a proof-of-concept refurbishing of a full commercial LAB, which recovered 35 % of its capacity. With a noteworthy capacity renewal and minimal release of hazardous materials, NH4Ac refurbishing promises to be an environment-friendly and economic alternative recycling paradigm for the LAB industry.

Direct capture of the alanine ghost in alanine-doped triglycine sulfate crystals.

In this report, ghostly ultra-trace amounts of alanine in alanine-doped triglycine sulfate crystal were directly observed by solid-state nuclear magnetic resonance, and the presence of two chemical states in the cation form and neutral form in the doped alanine was revealed. As the result, the crystal structure of alanine-doped triglycine sulfate was determined for the first time.

Effect of alkali metal sulfates on hydration properties of alpha-calcium sulfate hemihydrate for 3D printing

Three-dimensional printing (3DP) technology is an important means of achieving decorative convenience, personalization, and functional integration for future building construction. However, the setting time and hydration process of calcium sulfate hemihydrate (HH) present chanllenges for the 3DP application. This study aims to investigate the accelerating effect of alkali metal sulfates accelerators on the hydration transformation of HH into calcium sulfate dihydrate (DH). The setting time, conductivity, Ca2+ ion concentration, size distribution, and zeta (ζ) potential of gypsum slurries with different accelerators were measured. The results demonstrated that the accelerators significantly enhanced the hydration process of αlpha-calcium sulfate hemihydrate (α-HH). On the effect of accelerators, the setting times of gypsum slurries containing 30 wt% lithium sulfate (LS), sodium sulfate (NS) and potassium sulfate (KS) were accelerated by 82.56 %, 86.06 % and 97.13 %, respectively, compared to the control sample. The crystal particle sizes of hydration products decreased, and the absolute values of ζ potential increased to 1.85 mV, 3.1 mV, and 5.3 mV, respectively. The X-ray photoelectron spectroscopy (XPS) analysis revealed a shift in the peak values of the hardened specimens towards higher electric fields. This was accompanied by improved ion dispersion within the slurry, resulting in enhanced supersaturation of calcium sulfate dihydrate and crystallization of the crystal nuclei. Thus, the suitable accelerators can effectively achieve rapid solidification and hardening of high-fluidity gypsum slurries.

A biomacromolecular additive based on pullulan polysaccharide to enhance the life of lead-acid battery packs in DC systems

Abstract With the rapid growth in demand for mobile power, lead-acid batteries still occupy a large market share due to their excellence in energy storage. However, their lifespan is affected by various factors, which limits the application efficiency and environmental friendliness. In this regard, this paper proposes a method to enhance the service life of lead-acid battery packs by applying biomacromolecule additives. A lead-acid battery pack modification method is investigated by introducing chitosan, a natural macromolecule with excellent electrical conductivity and biodegradation properties, into lead-acid batteries. So that the chitosan-modified material forms a stable and protective film on the surface of the battery electrode plate, thereby reducing the analysis of sulphate crystals on the electrode surface. The method of modification of lead-acid battery packs has been studied. Comparative analysis of the experimental data shows that the modified battery pack exhibits lower charge transfer impedance and better electrochemical stability than the traditional lead-acid battery during the cyclic charge/discharge test. Through the cycle charge/discharge test, the energy loss of the battery with biomolecules is 30% lower than that of the unmodified battery, and the number of charge/discharge cycles increases by 60%, which effectively prolongs the service life of the lead-acid battery. The progress of this paper not only has guiding significance for the performance improvement of traditional lead-acid batteries but also provides a significant theoretical and experimental basis for the development and application of environmental friendly battery materials.

The Molecular Design of a Macrocycle Descaling Agent Based on Azacrown and the Mechanism of Barium Sulfate Scale Removal.

The formation of barium sulfate scale is a persistent and formidable challenge across various industrial processes. In order to effectively mitigate this problem, this study proposed the development of an innovative azacrown ether-based macrocycle descaling agent. Using density functional theory, an in-depth analysis of the surface energy of different barium sulfate crystal facets was carried out, together with a detailed investigation into the adsorption properties of the functional groups on the (001) surface. A further comprehensive investigation was carried out to determine how changes in the nitrogen and oxygen atoms in the crown ether framework influence its adsorption affinity to barium ions. In addition, a detailed analysis was carried out to elucidate the molecular interactions between crown ethers with pyridine carboxylic acid side chains and barium sulfate. The newly developed decalcifying macrocycle descaling agent exhibited superior adsorption performance, achieving an adsorption energy for barium ions approximately -4.1512 ev higher than that of conventional DTPA decalcifiers. This remarkable improvement is mainly attributed to the pivotal role of electrostatic forces in the coordination process between the macrocycle descaling agent and barium ions, with an electrostatic potential value reaching -143.37 kcal/mol. This discovery not only introduces a novel approach to the removal of barium sulfate scale but also highlights the significant potential of macrocycle chemistry in industrial applications.

Understanding the production and reduction of barium sulfate crystals through the use of additives and a controlled stirring rate

Barium sulfate crystals are minerals responsible for scaling in piping systems. Controlling the growth of these crystals can use additives (FeCl2 and SrCl2) and varying agitation speeds. The research was to optimize the impact of additives and agitation speed on the results of crystal form using RSM through Minitab 19 with Box-Behnken Design. The optimum conditions using additive FeCl2 at a concentration of 25 ppm, a stirring speed of 120 rpm for 30 minutes, and a coefficient of determination (R2) of 90.995 provided 0.4485 gr of barium sulfate crystals. The optimum conditions, however, used SrCl2 additives at a concentration of 20.2049 ppm and a stirring speed of 459.394 rpm for 30 minutes, yielding 0.4345 g of barium sulfates with a coefficient of determination (R2) of 91.41%. The results of crystallizing barium sulfate without additives appear to be superior to those obtained with additives in terms of production. In contrast, additives of FeCl2 and SrCl2 can inhibit barium sulfate formation, resulting in a reduction in crystal mass

Using multi‐component carbon composite as current collector in ultra‐battery

AbstractThis study introduces a multi‐component composite as a substitute for lead grids in ultra‐battery structures. The presented composite decreases the weight and simultaneously extends the cycle life of the traditional lead‐acid battery. Overall, UBZCP (the sample containing metal oxides and polyaniline), as the best sample, increases the cyclic stability by 3.3 and 1.4 times under high rate partial state of charge (HRPSoC) mode, compared to Native and UB450 samples. Metal oxides predominantly enhance the electrical conductivity of carbon‐based composites due to catalytic effects in the reduction of graphene oxide during heat treatment. Poly aniline shows considerably positive effect of electrochemical performance due to the high pseudo‐capacitive properties, high interaction of lead ions and the nitrogen in the polymer chains and accordingly hydrogen evolution reaction (HER) inhibition. The synergistic effect of polyaniline and metal oxides makes the best performance in the UBZCP sample achieve. Also, the UBZCP sample represented an enhancement of about 1.21 and 1.39 times in battery life and specific capacity under deep discharge mode compared to the Native sample. As a result, the introduced multi‐component composite making a 3D conductive network, facilitates Pb/PbSO4 reaction reversibility, and reduces the lead sulfate crystal size.

Insights into mechanism of electric field regulating calcium sulfate crystal structure and crystallization: A study by DFT calculation and experiment

Exploring the mechanism of external electric field (EF) regulating the structure and crystallization of calcium sulfate crystal is of great significance for solving the problem of inorganic salt scale in many industrial processes such as desalination and heat exchange. Here, the dispersion-corrected Density Functional Theory (DFT-D) calculations and a series of experiments were carried out to investigate the influence of EF on crystal structure, mechanical property and crystallization of gypsum crystal. The results show that under the influence of EF, the conventional cell of the gypsum crystal shortens in the direction of lattice parameter b. The water layer and the CaO8 octahedron are deformed. The stiffness and hardness of gypsum crystals decreases. The attachment energy and surface energy of (020) plane increase significantly. Both DFT-D calculations and experiment characterization results indicate that EF promotes a regular growth of gypsum crystal mainly along in the direction of (020) plane. Our study results demonstrate the possibility of electrical regulation of calcium sulfate crystal growth to solve the industrial calcium sulfate scale problem.

Numerical and experimental investigation of calcium sulfate crystallization fouling under upward subcooled flow boiling

In this paper, a quasi-unsteady mathematical model was presented to examine the crystallization fouling of the calcium sulfate aqueous solutions under upward subcooled flow boiling (SFB). An experimental set-up is also fabricated to collect experimental data for validating the model results. The developed model can axially and radially determine the temperature variation. An asymptotic predictive model was also used to calculate the heat transfer coefficients. Theoretical results of the bulk and surface temperatures at any desired location of the test section were coupled with the fouling formation equations to provide an integrated model for prediction of variable fouling resistance and deposit thickness along the heat transfer surface. Besides, variation of local heated surface and deposit surface temperatures as well as the pressure drop were theoretically evaluated over time while the deposit grows on the heated surface. The simulation results showed that reaction is the controlling mechanism when SFB is predominant.

Hardness, VSM, cyclic voltammetric and DFT studies of Cesium Sulphate-doped TGS crystals

The creation of capacitors, transducers, sensors, and infrared detectors utilise the nonlinear, ferroelectric triglycine sulphate (TGS) crystal. Cesium sulphate is incorporated into the lattice of TGS crystal to change its characteristics. Cesium sulfate-doped triglycine sulphate (CSTGS) single crystals were produced using a solution approach and a slow evaporation process. The title crystal was studied by single crystal XRD, FTIR, hardness, VSM, cyclic voltammetric and density functional theoretical (DFT) studies and the results are discussed in this paper.

Antisolvent crystallization of rare earth sulfate hydrates: Thermodynamics, kinetics and impact of iron

The thermodynamics and kinetics of ethanol antisolvent crystallization of rare earths from sulfate solutions has been explored, with a view towards separating the rare earths as part of a NdFeB magnet recycling process. The solubility of single and binary metal (Nd, Pr, Fe) phases in aqueous ethanol solutions has been determined. The impact of Fe and Pr on the crystallization of Nd is evaluated, the oxidation kinetics of Fe(II) to Fe(III) quantified, and the influence of Fe oxidation state on the thermodynamics and kinetics of crystallization investigated. Oxidation to Fe(III) is slow, with a half life of approx. 600 h. For pure Nd, the solubility of the obtained, stable sulphate octahydrate decreases exponentially with increased molar organic:aqueous (O/A) ratio, and is well described by the OLI model until O/A=0.2. Pr crystallizes as an isostructural octahydrate with similar solubility. Fe(II) precipitates as a mixed solid phase, with a solubility approximately 40 times higher than the rare earths at O/A=0.2. Fe(III) solutions exhibit liquid–liquid phase separation without precipitation at all evaluated concentrations. Nd and Pr coprecipitate together in proportion to their relative concentrations, with Pr precipitating at concentrations well below its pure component solubility. Fe(II) does not precipitate with Nd at O/A≤0.2 even at high concentration, with significant precipitation as separate particles at higher O/A for all concentrations. The crystallization kinetics and the morphology of the Nd phase is affected by the Fe oxidation state. The work highlights the potential of antisolvent crystallization for selective and efficient separation of REE from Fe.

Flow-Xl: a new facility for the analysis of crystallization in flow systems.

Characterization of crystallization processes in situ is of great importance to furthering knowledge of how nucleation and growth processes direct the assembly of organic and inorganic materials in solution and, critically, understanding the influence that these processes have on the final physico-chemical properties of the resulting solid form. With careful specification and design, as demonstrated here, it is now possible to bring combined X-ray diffraction and Raman spectroscopy, coupled to a range of fully integrated segmented and continuous flow platforms, to the laboratory environment for in situ data acquisition for timescales of the order of seconds. The facility used here (Flow-Xl) houses a diffractometer with a micro-focus Cu Kα rotating anode X-ray source and a 2D hybrid photon-counting detector, together with a Raman spectrometer with 532 and 785 nm lasers. An overview of the diffractometer and spectrometer setup is given, and current sample environments for flow crystallization are described. Commissioning experiments highlight the sensitivity of the two instruments for time-resolved in situ data collection of samples in flow. Finally, an example case study to monitor the batch crystallization of sodium sulfate from aqueous solution, by tracking both the solute and solution phase species as a function of time, highlights the applicability of such measurements in determining the kinetics associated with crystallization processes. This work illustrates that the Flow-Xl facility provides high-resolution time-resolved in situ structural phase information through diffraction data together with molecular-scale solution data through spectroscopy, which allows crystallization mechanisms and their associated kinetics to be analysed in a laboratory setting.

Simulation of Sodium Bicarbonate Purification via the Sodium Sulfate Carbonation Route

The present work sought to study the mother water of the process and point out alternatives so that the water present in this solution can be recovered and the possibility of recycling it can be analyzed. The following alternatives were adopted: the evaporation of water without reaching the saturation point of the mother water and evaporation beyond the saturation point. For the first case, flash distillation was used to remove unwanted components, followed by an evaporation process. The second case was studied employing salt crystallization, for which crystallizers were used. This study was conducted with Aspen Plus® v12 software, which can represent the desired route, in addition to having data and tools that are suitable for the process modeling and simulation. For the evaporation without crystallization, it was noticed that it was possible to remove 23.89% of the water from the mother water. For the crystallization case, it was found that the mother water solution had dissolved ammonium sulfate for crystallization; however, it was necessary to first precipitate sodium sulfate. In the crystallization of sodium sulfate, it was possible to remove 85.62% of vapor from the mother water solution, containing water, ammonia, and carbon dioxide, thus inferring the possibility of recycling this current to the process. This study shows that it is not appropriate to insert evaporation equipment without thinking about the precipitation of by-products since there would be an increase in the price of the route, with little raw material for reuse.

Control Over the Non‐Classical Crystallization of Calcium Sulfate by Rationally Selected Self‐Assembling Peptides

Control Over the Non‐Classical Crystallization of Calcium Sulfate by Rationally Selected Self‐Assembling Peptides

Spontaneous piezoeletric effect as evidence of ferroelastoelectricity in guanidine zinc sulfate crystal

The crystal of [C(NH2)3]2Zn(SO4)2 guanidine zinc sulfate was grown and its structure, dilatometric, dielectric, elastic and piezoelectric properties were studied in a broad temperature range, covering the phase transition point. The crystal undergoes a continuous phase transition at 178 K from the room temperature tetragonal phase with a space group I4¯2d\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ ext{I}\\overline{4}2\ ext{d }$$\\end{document} to the tetragonal low temperature phase with a space group I4¯\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ ext{I}\\overline{4 }$$\\end{document}. The structural X-ray studies allowed proposing molecular mechanism associated with the rearrangement in the configuration of N–H⋯O hydrogen bonds and reorientation of guanidine cations in the structure, leading to a change in the symmetry of the low temperature phase. Results of thermal expansion and dielectric studies are typical of a structural nonferroelectric continuous transition. Also measurement of piezoelectric and elastic properties revealed small anomalies at 178 K. Below the transition temperature, a new piezoelectric component, that is a ferroelastoelectric macroscopic order parameter, was found.

A bioinspired doxorubicin-carried albumin Nanocage against aggressive Cancer via systemic targeting of tumor and lymph node metastasis

Cancer metastasis and recurrence are obstacles to successful treatment of aggressive cancer. To address this challenge, chemotherapy is indispensable as an essential part of comprehensive cancer treatment, particularly for subsequent therapy after surgical resection. However, small-molecule drugs for chemotherapy always cause inadequate efficacy and severe side effects against cancer metastasis and recurrence caused by lymph node metastases. Here, we developed doxorubicin-carried albumin nanocages (Dox-AlbCages) with appropriate particle sizes and pH/enzyme-responsive drug release for tumor and lymph node dual-targeted therapy by exploiting the inborn transport properties of serum albumin. Inspired by the protein-templated biomineralization and remote loading of doxorubicin into liposomes, we demonstrated the controlled synthesis of Dox-AlbCages via the aggregation or crystallization of doxorubicin and ammonium sulfate within albumin nanocages using a biomineralization strategy. Dox-AlbCages allowed efficient encapsulation of Dox in the core protected by the albumin corona shell, exhibiting favorable properties for enhanced tumor and lymph node accumulation and preferable cellular uptake for tumor-specific chemotherapy. Intriguingly, Dox-AlbCages effectively inhibited tumor growth and metastasis in orthotopic 4T1 breast tumors and prevented postsurgical tumor recurrence and lung metastasis. At the same time, Dox-AlbCages had fewer side effects than free Dox. This nanoplatform provides a facile strategy for designing tumor- and lymph node-targeted nanomedicines for suppressing cancer metastasis and recurrence.