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Keywords = amphoteric clay

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18 pages, 6084 KB  
Article
Amphoteric Halloysite and Sepiolite Adsorbents by Amino and Carboxy Surface Modification for Effective Removal of Cationic and Anionic Dyes from Water
by Boutaina Boumhidi, Nadia Katir, Jamal El Haskouri, Khalid Draoui and Abdelkrim El Kadib
Minerals 2025, 15(8), 841; https://doi.org/10.3390/min15080841 - 8 Aug 2025
Viewed by 430
Abstract
Surface functionalization is a key enabler that imparts solid materials with excellent chemoselectivity. With this aim, halloysite and sepiolite clay particles were functionalized with carboxyethylsilanetriol sodium salt (CES) and 3-aminopropyltriethoxysilane (APTES), affording carboxy-terminated and amino-terminated clay, respectively. In the case of halloysite, the [...] Read more.
Surface functionalization is a key enabler that imparts solid materials with excellent chemoselectivity. With this aim, halloysite and sepiolite clay particles were functionalized with carboxyethylsilanetriol sodium salt (CES) and 3-aminopropyltriethoxysilane (APTES), affording carboxy-terminated and amino-terminated clay, respectively. In the case of halloysite, the grafting occurs at Al-OH groups of the lumen surface (tube inner surface) and Al-OH and Si-OH groups at the edges and external surface defects of the nanotubes. For sepiolite, silanol groups located on the edges of the structural channels were at the origin of a chemical reaction between this fibrous clay and the terminal alkoxysilane. The resulting modified clays were examined for removal of Congo red (CR) and malachite green (MG) as anionic and cationic dyes, respectively. Clay bearing only carboxylic groups display more affinity towards cationic dye (MG), recording 926 mg·g−1 and 387 mg·g−1 for HNT-CES and SEP-CES, respectively, while amino-functionalized clays show very high adsorption for anionic dye (CR), reaching 1232 and 1228 mg·g−1 for HNT-APTES and SEP-APTES, respectively. Simultaneous grafting of the two silyl coupling reagents was also attempted through one-pot and sequential grafting method, with the latter being more appropriate to access amphoteric clay featuring both carboxylic and amino groups. The behavior of the bifunctional adsorbents was investigated with respect to pristine and monofunctional clay. The obtained results provide insights to fulfill the requirement for handling complex water effluent containing both anionic and cationic pollutants, towards more sustainable development. Full article
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20 pages, 4197 KB  
Article
Removal of Lead Cations by Novel Organoclays Derived from Bentonite and Amphoteric and Nonionic Surfactants
by Maria Gertsen, Leonid Perelomov, Anna Kharkova, Marina Burachevskaya, S. Hemalatha and Yury Atroshchenko
Toxics 2024, 12(10), 713; https://doi.org/10.3390/toxics12100713 - 30 Sep 2024
Cited by 3 | Viewed by 1643
Abstract
For many decades, natural and modified clay minerals have been used as adsorbents to clean up aquatic and soil ecosystems contaminated with organic and inorganic pollutants. In this study, organoclays based on bentonite and various amphoteric and nonionic surfactants were synthesized and tested [...] Read more.
For many decades, natural and modified clay minerals have been used as adsorbents to clean up aquatic and soil ecosystems contaminated with organic and inorganic pollutants. In this study, organoclays based on bentonite and various amphoteric and nonionic surfactants were synthesized and tested as effective sorbents for lead ions. The maximum values of R were obtained when describing the sorption processes using the Langmuir model, which ranged from 0.97 to 0.99. The adsorption of lead ions by these organoclays was investigated using different sorption models including the Langmuir, Freundlich, and BET. It was found that, according to the values of limiting adsorption to the Langmuir equation, the synthesized organoclays formed an increasing series: organoclay with cocamide diethanolamine < bentonite < organoclay with lauramine oxide < organoclay with sodium cocoiminodipropionate < organoclay with disodium cocoamphodiacetate < organoclay with alkyl polyglucoside. The Gibbs energy for all of the analyzed samples was calculated and found to be negative, indicating the spontaneity of the cation adsorption process in the forward direction. The maximum value of the adsorption capacity of lead cations on organoclay-based bentonite with alkyl polyglucoside was 1.49 ± 0.05 mmol/g according to the Langmuir model, and 0.523 ± 0.003 mmol/g as determined by the BET model. In the process of modifying bentonite, there was an increase in negative values of the zeta potential for organoclays compared to the initial mineral, which clearly enhanced their electrostatic interactions with the positively charged lead ions. It was hypothesized, based on the physicochemical principles, that exchange adsorption is the main mechanism for lead absorption. Based on chemical approaches, organoclays based on amphoteric surfactants absorb lead mainly through the mechanisms of electrostatic attraction, ion exchange, and complexation as well as the formation of insoluble precipitates. Organoclays based on nonionic surfactants, on the other hand, absorb lead through mechanisms of complexation (including chelation) and the formation of insoluble chemical precipitates. The comparison of isotherms from different models allows us to find the most accurate match between the model and the experimental data, and to better understand the nature of the processes involved. Full article
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20 pages, 10304 KB  
Article
Chemical and Physical Characterization of Three Oxidic Lithological Materials for Water Treatment
by José G. Prato, Fernando Millán, Marin Senila, Erika Andrea Levei, Claudiu Tănăselia, Luisa Carolina González, Anita Cecilia Ríos, Luis Sagñay Yasaca and Guillermo Eduardo Dávalos
Sustainability 2024, 16(18), 7902; https://doi.org/10.3390/su16187902 - 10 Sep 2024
Cited by 1 | Viewed by 1393
Abstract
Water treatment necessitates the sustainable use of natural resources. This paper focuses on the characterization of three oxidic lithological materials (OLMs) with the aim of utilizing them to prepare calcined adsorbent substrates for ionic adsorption. The three materials have pH levels of [...] Read more.
Water treatment necessitates the sustainable use of natural resources. This paper focuses on the characterization of three oxidic lithological materials (OLMs) with the aim of utilizing them to prepare calcined adsorbent substrates for ionic adsorption. The three materials have pH levels of 7.66, 4.63, and 6.57, respectively, and organic matter contents less than 0.5%. All of the materials are sandy loam or loamy sand. Their electric conductivities (0.18, 0.07, and 0.23 dS/m) show low levels of salinity and solubility. Their CEC (13.40, 13.77, and 6.76 cmol(+)kg) values are low, similar to those of amphoteric oxides and kaolin clays. Their aluminum contents range from 7% up to 12%, their iron contents range from 3% up to 7%, their titanium contents range from 0.3% to 0.63%, and their manganese contents range from 0.007% up to 0.033%. The amphoteric oxides of these metals are responsible for their ionic adsorption reactions due to their variable charge surfaces. Their zirconium concentrations range from 100 to 600 mg/g, giving these materials the refractory properties necessary for the preparation of calcined adsorbent substrates. Our XRD analysis shows they share a common mineralogical composition, with quartz as the principal component, as well as albite, which leads to their thermal properties and mechanical resistance against abrasion. The TDA and IR spectra show the presence of kaolinite, which is lost during thermal treatments. The results show that the OLMs might have potential as raw materials to prepare calcined adsorbent substrates for further applications and as granular media in the sustainable treatment of both natural water and wastewater. Full article
(This article belongs to the Section Environmental Sustainability and Applications)
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21 pages, 9002 KB  
Review
Organoclays Based on Bentonite and Various Types of Surfactants as Heavy Metal Remediants
by Leonid Perelomov, Maria Gertsen, Marina Burachevskaya, S. Hemalatha, Architha Vijayalakshmi, Irina Perelomova and Yurii Atroshchenko
Sustainability 2024, 16(11), 4804; https://doi.org/10.3390/su16114804 - 5 Jun 2024
Cited by 11 | Viewed by 3633
Abstract
The rapid industrial development of civilization has led to the need for the development of new materials to clean up chemically contaminated wastewater and soils. Organoclays, based on smectite minerals and various types of surfactants, are one of the most effective sorbents for [...] Read more.
The rapid industrial development of civilization has led to the need for the development of new materials to clean up chemically contaminated wastewater and soils. Organoclays, based on smectite minerals and various types of surfactants, are one of the most effective sorbents for adsorbing organic and inorganic pollutants. Organoclays are clay minerals that have been modified by the intercalation or grafting of organic molecules. The main mechanism of interaction between organic substances and organoclays involves the adsorption of the substances onto the surface of the clay mineral, which has an expanded structural cell. Various types of surfactants can be used to synthesize organoclays, including cationic, anionic, and amphoteric surfactants. Each type of surfactant has different properties that affect the clay’s ability to sorb. Cationic forms of trace elements, such as heavy metals, can also be adsorbed by organoclays. Data on the adsorption of these substances by organoclays are provided, along with information on how to synthesize them using various surfactants. This review also discusses the main mechanisms of interaction between these substances and clays and the various methods used to create organoclays. It is clear that the adsorption of heavy metals by organoclays is not influenced by their structure or properties, as they belong to the category of surfactant, but rather by their overall chemical structure and characteristics. The wide variety of surfactant types leads to different effects on the adsorption properties of trace elements. Full article
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13 pages, 9045 KB  
Article
A Novel Amphoteric Ion-Modified, Styrene-Based Nano-Microsphere and Its Application in Drilling Fluid
by Xianfa Zhang, Jingping Liu, Jinsheng Sun, Zonglun Wang, Zhiwen Dai, Yuanwei Sun and Taifeng Zhang
Materials 2023, 16(18), 6096; https://doi.org/10.3390/ma16186096 - 6 Sep 2023
Cited by 2 | Viewed by 1483
Abstract
With the gradual depletion of shallow oil and gas, deep oil and gas has become the focus of development. However, deep formations generally face the challenge of high-temperature and high-salinity, and drilling fluid agents are prone to failure, leading to drilling fluid intrusion [...] Read more.
With the gradual depletion of shallow oil and gas, deep oil and gas has become the focus of development. However, deep formations generally face the challenge of high-temperature and high-salinity, and drilling fluid agents are prone to failure, leading to drilling fluid intrusion into the formation that can cause serious drilling accidents such as well bore collapse. For this, a styrene-based nano-microsphere (SSD) modified with amphoteric ions was developed, with a particle size of 228 nm which could resist temperatures up to 200 °C and sodium chloride (NaCl) up to saturation. SSD has significant salt-responsive properties and its aqueous dispersion becomes transparent with increasing salinity. The SSD provided superior plugging performance in solutions containing NaCl, with a core plugging efficiency of 95.2%, and it was significantly better than the anion-modified microspheres. In addition, in drilling fluids under high temperature and high-salinity conditions, the SSD promotes particle gradation of drilling fluids and improves the zeta potential through its own plugging and synergistic effect with clay, which significantly improves the comprehensive performance of drilling fluids, such as stability, rheological performance, and filtration reduction performance. The development of SSD provides a new idea for research of high-temperature and high-salinity-resistant drilling fluid agents. Full article
(This article belongs to the Special Issue Advances in Natural Rocks and Their Composite Materials)
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21 pages, 5204 KB  
Article
Laponite Composites: In Situ Films Forming as a Possible Healing Agent
by Ramón Andrés Pineda-Álvarez, Carolina Flores-Avila, Luis Medina-Torres, Jesús Gracia-Mora, José Juan Escobar-Chávez, Gerardo Leyva-Gómez, Mohammad-Ali Shahbazi and María Josefa Bernad-Bernad
Pharmaceutics 2023, 15(6), 1634; https://doi.org/10.3390/pharmaceutics15061634 - 31 May 2023
Cited by 3 | Viewed by 2844
Abstract
A healing material must have desirable characteristics such as maintaining a physiological environment, protective barrier-forming abilities, exudate absorption, easy handling, and non-toxicity. Laponite is a synthetic clay with properties such as swelling, physical crosslinking, rheological stability, and drug entrapment, making it an interesting [...] Read more.
A healing material must have desirable characteristics such as maintaining a physiological environment, protective barrier-forming abilities, exudate absorption, easy handling, and non-toxicity. Laponite is a synthetic clay with properties such as swelling, physical crosslinking, rheological stability, and drug entrapment, making it an interesting alternative for developing new dressings. This study evaluated its performance in lecithin/gelatin composites (LGL) as well as with the addition of maltodextrin/sodium ascorbate mixture (LGL MAS). These materials were applied as nanoparticles, dispersed, and prepared by using the gelatin desolvation method—eventually being turned into films via the solvent-casting method. Both types of composites were also studied as dispersions and films. Dynamic Light Scattering (DLS) and rheological techniques were used to characterize the dispersions, while the films’ mechanical properties and drug release were determined. Laponite in an amount of 8.8 mg developed the optimal composites, reducing the particulate size and avoiding the agglomeration by its physical crosslinker and amphoteric properties. On the films, it enhanced the swelling and provided stability below 50 °C. Moreover, the study of drug release in maltodextrin and sodium ascorbate from LGL MAS was fitted to first-order and Korsmeyer–Peppas models, respectively. The aforementioned systems represent an interesting, innovative, and promising alternative in the field of healing materials. Full article
(This article belongs to the Special Issue Carbohydrate-Based Carriers for Drug Delivery)
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20 pages, 2358 KB  
Article
Micro-Analytical Study of a Zeolites/Geo-Polymers/Quartz Composite, Dielectric Behaviour and Contribution to Brønsted Sites Affinity
by Abdel Boughriet, Oscar Allahdin, Nicole Poumaye, Gregory Tricot, Bertrand Revel, Ludovic Lesven and Michel Wartel
Ceramics 2022, 5(4), 908-927; https://doi.org/10.3390/ceramics5040066 - 2 Nov 2022
Cited by 4 | Viewed by 2379
Abstract
The chemical and mineralogical surface properties of a brick-derived composite were examined by using an environmental scanning electron microscopy (ESEM) equipped with an energy dispersive X-ray spectrometer (EDS). Investigations revealed that the material could be assimilated to an adsorptive membrane having zeolites deposited [...] Read more.
The chemical and mineralogical surface properties of a brick-derived composite were examined by using an environmental scanning electron microscopy (ESEM) equipped with an energy dispersive X-ray spectrometer (EDS). Investigations revealed that the material could be assimilated to an adsorptive membrane having zeolites deposited onto quartz matrix. In our calculation, the membrane was considered as a diphase composite and its dielectric constant was evaluated from theoretical models developed in the literature. Electro-kinetic analysis showed that composite surfaces were hydroxylated with the formation of hydroxyl groups which behaved amphoterically. A theory-based approach was used for calculating thermodynamic constants relative to surface-protonation equilibriums. In the H-form of the composite, the occurrence of bridging Si–(OH)–Al sites were evidenced by mathematical calculations utilizing equations in direct relation to mineralogical, crystallographic and dielectric surface characteristics. 1H MAS NMR spectroscopy confirmed the existence of bridging Brønsted acid sites at acidified composite surfaces interacting with ammonium (as probe ions). Owing to advancements in brick-based composites research, this should lead more to the development of “ceramic” adsorptive membranes with natural clay materials. Full article
(This article belongs to the Special Issue Advances in Ceramics)
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8 pages, 1909 KB  
Communication
Comparative Study of the Hydrophobicity of Organo-Montmorillonite Modified with Cationic, Amphoteric and Nonionic Surfactants
by Georgy Lazorenko, Anton Kasprzhitskii and Victor Yavna
Minerals 2020, 10(9), 732; https://doi.org/10.3390/min10090732 - 19 Aug 2020
Cited by 26 | Viewed by 4163
Abstract
In this work, a series of comparative studies for the effect of the nine commercially available cationic, amphoteric and nonionic surfactants on the structure and wettability of the montmorillonite based organoclays were performed. The pristine and modified clays were characterized by X-ray diffraction [...] Read more.
In this work, a series of comparative studies for the effect of the nine commercially available cationic, amphoteric and nonionic surfactants on the structure and wettability of the montmorillonite based organoclays were performed. The pristine and modified clays were characterized by X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and water contact angle (CA) measurements. It has been observed that the maximum basal spacing and the hydrophobicity of the organoclays increased with the alkyl chain length and chain number of the surfactant. It was found out that this effect is most pronounced when using cationic surfactants. The maximum value of contact angle corresponded to the organoclay obtained using di(hydrogenated tallow) ammonium chloride (DDA). The outcomes of this study are important and relevant to the preparation of effective organoclays for geotechnical, petroleum and polymer nanocomposite applications. Full article
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18 pages, 4879 KB  
Article
Authigenic Clay Minerals from Interface Reactions of Concrete-Clay Engineered Barriers: A New Perspective on Mg-Clays Formation in Alkaline Environments
by Jaime Cuevas, Ana Isabel Ruiz, Raúl Fernández, Daniel González-Santamaría, María Angulo, Almudena Ortega, Elena Torres and María Jesús Turrero
Minerals 2018, 8(9), 362; https://doi.org/10.3390/min8090362 - 21 Aug 2018
Cited by 17 | Viewed by 4944
Abstract
Artificial and singular geochemical environments are created around the engineered barrier systems (EBS) designed to isolate high level nuclear wastes in deep geological repositories. A concrete-bentonite interface takes place within the EBS and it builds a significant chemical gradient (pH), approximately from pH [...] Read more.
Artificial and singular geochemical environments are created around the engineered barrier systems (EBS) designed to isolate high level nuclear wastes in deep geological repositories. A concrete-bentonite interface takes place within the EBS and it builds a significant chemical gradient (pH), approximately from pH 8 (bentonite) to pH 12 (low alkali concrete), in a few millimetre thickness. This disequilibrium triggers dissolution and precipitation reactions and form a thin altered region. In this area, poorly ordered authigenic clay minerals, mainly hydrated magnesium silicates, are formed adjacent to hydrated calcium silicates and calcite precipitates adhered to the interface with concrete. This paper presents the development of this authigenic mineral layer comparing 6–18 months to 13 years interfaces. Scanning Electron Microscopy with Energy Dispersive X-ray spectroscopy (SEM-EDX) morphological and chemical characterization with the aid of ternary plots, X-ray diffraction (XRD) and infrared (IR) data show the young to old interface evolution from single brucite layers to stevensite-saponite silicates composition. Geochemical calculations indicate that this layer acts as a pH~11 buffer useful to minimize bentonite alteration and to favour the retention of amphoteric metal ions. Full article
(This article belongs to the Special Issue Authigenic Clay Minerals: Mineralogy, Geochemistry and Applications)
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