Rothish R. Nair , Sayoojya P. Sathyan , K.P. Prathish
{"title":"Development of free flowing granular hybrid functionalized clay sorbent filters for chromium removal from waste water","authors":"Rothish R. Nair , Sayoojya P. Sathyan , K.P. Prathish","doi":"10.1016/j.clay.2024.107591","DOIUrl":"10.1016/j.clay.2024.107591","url":null,"abstract":"<div><div>Chromium (VI) contamination in water resources at industrial sites poses significant environmental and health risks. Conventional sorbents often suffer from limitations such as clogging, back pressure, poor kinetics, and challenges in coupling with flow systems and regeneration. This study focuses on developing, characterizing, and applying free-flowing granular (FFG) amidoxime-functionalized montmorillonite (Mt) clay sorbents (AO-Mt-H-C) to enhance chromium (VI) removal from contaminated waste water. Batch adsorption experiments demonstrated that AO-Mt-H-C outperformed montmorillonite clay modified with quaternary ammonium alone (Mt-H-C), achieving a Cr (VI) removal efficiency of 50.6 mg g<sup>−1</sup> compared to 44.3 mg g<sup>−1</sup>, due to the synergistic interactions of quaternary ammonium and amidoxime functionalities. To address the limitations of conventional sorbents, such as clogging and poor kinetics, an FFG filter column was developed and tested, showing effective Cr (VI) removal across various water sources with minimal interference in drinking and groundwater. In industrial wastewater with higher matrix loads, over 99 % removal efficiency was achieved with a 25 % increase in sorbent dosage. Desorption and reusability assessments confirmed the AO-Mt-H-C's effectiveness across three cycles. Mathematical modelling using Thomas and Yoon–Nelson equations supported the design of customized treatment systems. Scalability was demonstrated by treating 1.6 m<sup>3</sup> of textile industrial effluents (100 mg L<sup>−1</sup> Cr (VI)) with quantitative removal efficiency (>99.5 %). This study illustrates that the hybrid functionalization and free-flowing granulation of clay sorbent materials significantly enhance Cr (VI) removal, providing valuable insights for advanced water pollution mitigation and environmental sustainability.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107591"},"PeriodicalIF":5.3,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liyan Wang , Keqi Huang , Zi Yang , Rudolph Buchheit , Zhiyuan Feng
{"title":"Research on the corrosion protection of in-situ prepared LiAl layered double hydroxides on AZ31 Mg alloy under standard atmospheric pressure and low temperature","authors":"Liyan Wang , Keqi Huang , Zi Yang , Rudolph Buchheit , Zhiyuan Feng","doi":"10.1016/j.clay.2024.107585","DOIUrl":"10.1016/j.clay.2024.107585","url":null,"abstract":"<div><div>This work successfully prepared Li<img>Al LDHs coatings on AZ31 Mg alloy under standard atmospheric pressure and low temperature. The whole process did not require a hydrothermal autoclave reactor and high pressure. Electrochemical test results showed that the coating was able to provide good corrosion protection performance. The Li<img>Al LDHs coatings provided a large low-frequency impedance on AZ31. When the treatment time was 24 h, the maximum <em>|Z|</em><sub>0.01Hz</sub> at pH = 12 was 5.14 × 10<sup>4</sup> Ω∙cm<sup>2</sup>, which is more than an order of magnitude higher than the <em>|Z|</em><sub>0.01Hz</sub> of 1.81 × 10<sup>3</sup> Ω∙cm<sup>2</sup> for the bare sample. Under the same treatment conditions, the potentiodynamic polarization test results showed that the Li<img>Al LDHs coated samples had a lower corrosion current density and a higher breakdown potential. The <em>i</em><sub>corr</sub> was 1.78 × 10<sup>−7</sup> A/cm<sup>2</sup> and <em>E</em><sub>br</sub> was −0.82 V<sub>SCE</sub> compared to the Mg substrate (<em>i</em><sub>corr</sub> of 1.13 × 10<sup>−5</sup> A/cm<sup>2</sup> and <em>E</em><sub>br</sub> of −1.53 V<sub>SCE</sub>). Additionally, Li<img>Al LDHs coatings also had a significant inhibitory effect on cathodic hydrogen evolution, providing targeted protection to the cathodic areas.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107585"},"PeriodicalIF":5.3,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiaxin Liu , Chentao Zhu , Xiong Yu (Bill) , Chanjuan Han
{"title":"Mitigating desiccation cracking in bentonite using novel microencapsulated phase change materials","authors":"Jiaxin Liu , Chentao Zhu , Xiong Yu (Bill) , Chanjuan Han","doi":"10.1016/j.clay.2024.107586","DOIUrl":"10.1016/j.clay.2024.107586","url":null,"abstract":"<div><div>Bentonite, widely employed in geotechnical projects, faces a pressing challenge in addressing desiccation cracking. Leveraging its high latent heat, microencapsulated phase change material (microPCM) holds promise in ameliorating this issue. This study pioneers the application of microPCM as an additive to enhance bentonite's resistance to cracking. Employing an automated measurement platform, a series of desiccation cracking tests were conducted on bentonite blends with varying microPCM contents. Techniques including mercury intrusion porosimetry, scanning electron microscopy, digital image processing, infrared thermography, and particle image velocimetry, were employed to elucidate these mechanisms. Quantitative metrics were defined and meticulously analyzed across samples with different microPCM ratios. Additionally, qualitative and quantitative assessments of pore structure features were conducted. Key findings demonstrate that the incorporation of microPCM can delay evaporation by up to 33 % (at a microPCM mass fraction of 15 %) while intensifying volumetric contraction. This delay effectively postpones crack initiation and doubles crack propagation duration. However, microPCM agglomeration tendencies leading to formation of additional cavities may act as initial defects in the bentonite. This study not only illuminates the potential of microPCM as an effective additive in enhancing bentonite's resistance to desiccation cracking but also identifies associated challenges, thus paving the way for further innovative research.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107586"},"PeriodicalIF":5.3,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Early-age shrinkage behavior of cement mixtures regulated with metakaolin-based internal conditioning","authors":"Dayou Luo, Jianqiang Wei","doi":"10.1016/j.clay.2024.107583","DOIUrl":"10.1016/j.clay.2024.107583","url":null,"abstract":"<div><div>Shrinkage occurs in concrete during its hardening and strength gain process leading to undesired deformation, cracking, and decreases in strength and durability. While metakaolin-based internal conditioning (MIC) has been validated as a promising technique for modifying cement and mitigating alkali-silica reactions in concrete, its impact on the early-age shrinkage behavior of cement remains unexplored. This study delves into the effects of MIC and its coupling with lithium on the chemical shrinkage, autogenous shrinkage, and drying shrinkage of portalnd cement incorporating 30 % metakaolin with varying degrees of saturation (50 %, 75 %, and 100 %). The results indicate that the hydration of cement can be substantially enhanced by MIC with 29.0 % more heat released and a 32.3 % decrease in calcium hydroxide content. As a result of the enhanced hydration, cement with MIC yielded increased chemical shrinkage. Compared with dry MK, the autogenous shrinkage and drying shrinkage of cement were decreased by 38.0 % and 11.0 %, respectively, in the presence of MIC. A synergistic effect between MIC and lithium was suggested by the higher efficacy in suppressing autogenous shrinkage.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107583"},"PeriodicalIF":5.3,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gaokuo Du, Huanrong Li, Zixuan Li, Xinchi Ye, Yige Wang
{"title":"Luminescence Boosting after adding Quaternary ammonium/Phosphine Cations to Europium (III) Laponite Clay","authors":"Gaokuo Du, Huanrong Li, Zixuan Li, Xinchi Ye, Yige Wang","doi":"10.1016/j.clay.2024.107584","DOIUrl":"10.1016/j.clay.2024.107584","url":null,"abstract":"<div><div>Quaternary ammonium/phosphine cations added to the platelets of Laponite clay can lead to the remarkable enhancement of luminescence efficiency of the europium (III) β-diketonate complex. The mechanism for the luminescence boosting by the organic cations was elucidated by comparing two diketonate ligands with different pKa and the pH value of the selected organic salts based on the stationery and time resolved spectroscopy. It can be concluded as that the presence of the quaternary ammonium or quaternary phosphine cations helps to form Eu<sup>3+</sup>-β-diketonate complexes with high coordination numbers by decreasing the acidic sites on the platelet surface of laponite clay. Our work further strengthens the simplicity and generalization of obtaining highly luminescent materials and provides a unique insight into the function of the quaternary ammonium/quaternary phosphine cations in boosting the luminescence of lanthanide-based organic-inorganic hybrid materials.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107584"},"PeriodicalIF":5.3,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142358961","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zheng Wang , Yue Qiu , Baoyu Zou , Deke Wang , Zifei Gao , Xuanheng Zhang , Juanjuan Ma , Lin Liu , Chao Liu , Zhiwei Tong
{"title":"Efficient transformation of CO2 into α-alkylidene cyclic carbonates over Cu0/Cu+ derived from CuAl layered double hydroxide/reduced graphene oxide hybrid","authors":"Zheng Wang , Yue Qiu , Baoyu Zou , Deke Wang , Zifei Gao , Xuanheng Zhang , Juanjuan Ma , Lin Liu , Chao Liu , Zhiwei Tong","doi":"10.1016/j.clay.2024.107581","DOIUrl":"10.1016/j.clay.2024.107581","url":null,"abstract":"<div><div>A simple liquid-phase co-precipitation method was used to achieve a good dispersion of CuAl layered double hydroxide (CuAl-LDH) on the surface of graphene oxide (GO), and Cu<sup>2+</sup> in the lattice of CuAl-LDH was in-situ reduced to Cu<sup>0</sup> and Cu<sup>+</sup> species, resulting in the preparation of R-CuAl-LDH/rGO catalyst. It could effectively catalyze the cyclization of CO<sub>2</sub> and propargylic alcohols under mild conditions (50 °C and 1 bar), and the yield exceeded 99 % within only 40 min. Systematic characterization revealed that two-dimensional LDH nanosheets were grown on the rGO surface in an irregular orientation, leading to a higher specific surface area and more abundant surface active sites. Meanwhile, the synergistic catalysis of Cu<sup>0</sup> and Cu<sup>+</sup> dual-active sites greatly enhanced the catalytic efficiency. In addition, the catalyst had excellent recycling properties with no significant loss of activity after 5 cycles of continuous operation.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107581"},"PeriodicalIF":5.3,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142359046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Compressibility of a binary bentonite-based mixture with particular emphasis on pellet orientation","authors":"Arisleidy Mesa-Alcantara , Enrique Romero , Joel Torres-Serra , Nadia Mokni","doi":"10.1016/j.clay.2024.107575","DOIUrl":"10.1016/j.clay.2024.107575","url":null,"abstract":"<div><div>Binary mixtures of Wyoming-type bentonite, consisting of 80 % mass high-density pellets and 20 % granular bentonite, are currently considered candidate materials for the French concept of vertical sealing systems for deep and long-term disposal of radioactive wastes. At low emplacement water contents, the hydro-mechanical behaviour is primarily controlled by contact forces between pellets, forming a coarse grain-supported structure over which granular bentonite is poured. These pellets were uniaxially compacted at elevated stresses to reach high dry densities. Subsequent pellet unloading resulted in anisotropic features due to fissuring and delamination, followed by water absorption. This study investigated compressibility changes upon loading under laterally confined conditions of a well-oriented pellet-supported structure, mimicking the setup of the <em>in situ</em> VSEAL 1 experiment at Tournemire (France). Two pellet orientations at the same dry density and coordination number of pellet contacts were examined in a pure pellet skeleton and a mixture to account for potential heterogeneity during pouring. A discrete element method was used to simulate the compression results with pellets represented as a clump with a heterogeneous void ratio distribution due to fissuring. These simulations were instrumental in understanding the important anisotropic deformation properties of pellet-supported structures under two distinct orientations.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107575"},"PeriodicalIF":5.3,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142328357","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Chemometrics of meta-clay FT-IR spectra: From heating temperature estimation to meta-clay identification","authors":"Matthieu Ménager","doi":"10.1016/j.clay.2024.107579","DOIUrl":"10.1016/j.clay.2024.107579","url":null,"abstract":"<div><div>In this research, chemometric tools (Partial Least-Squares Regression, Principal Component Regression, Linear Discriminant Analysis for example) allowed estimating firing temperatures and to identify the type of meta-clay based on their infrared spectra.</div><div>The 3 min phases observed in clay thermal degradation were: (i) a dehydroxylation reaction between 400 and 500–600 °C leading to the formation of a non-crystalline meta-clay, (ii) a continuous thermal degradation reaction of the meta-clay involving the Si<img>O bonds between 500 and 850 °C, (iii) the formation of secondary silicates above 850 °C.</div><div>The 10 Latent Variables of the Partial Least-Squares Regression model led to accurate predictions (Root Mean Squared Error of Prediction = 66.6) and provided a good correlation between predicted and actual temperatures, without any estimation bias related to the type of clay, the presence of other minerals or iron concentration. These models give greater importance to the infrared absorption bands of the bonds involved in thermal degradation: Si-O-Si (1026 and 461 <span><math><mi>c</mi><msup><mi>m</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>), Si-O-Al (526 <span><math><mi>c</mi><msup><mi>m</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>), Si<img>O or Al<img>O (1095 <span><math><mi>c</mi><msup><mi>m</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>), and infrared bands resulting from the formation of meta-clays (486 et 562 <span><math><mi>c</mi><msup><mi>m</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>).</div><div>Finally, a Linear Discriminant Analysis model is proposed in order to identify the type of meta-clay between different types of meta-kaolinites, meta-nacrite and meta-smectite in 96 % of cases. The meta-clays produced by the firing of halloysite, dickite and kaolinite were too close in terms of infrared spectra to be distinguished.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107579"},"PeriodicalIF":5.3,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142323853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Thermal evolution of a kaolin: Quantitative phase analysis and assessment of the thermal markers of the Provins clay","authors":"Gilles Wallez , Anne Bouquillon , Yvan Coquinot","doi":"10.1016/j.clay.2024.107582","DOIUrl":"10.1016/j.clay.2024.107582","url":null,"abstract":"<div><div>The thermal evolution of a kaolin from Provins, France, has been monitored using X-ray diffraction and Rietveld analysis over the 950–1200 °C range. The quantitative assessment of the evolution of mullite, cristobalite and the transient spinel was made possible by the recent resolution of the crystal structure of the latter phase, thus leading to investigate and explain its two-step nucleation mechanism. The progressive transformation of anatase (TiO<sub>2</sub>) into rutile was measured the same way, along with the mean crystallite size and cell parameters evolution of mullite. These transformations were then discussed in order to propose relevant thermal markers likely to be used to assess the thermal treatments undergone by kaolinite-based ceramics. In the present case, the rutile/anatase ratio turned to be relevant up to 1100 °C, mullite's <em>a</em> parameter in the domain of crystallization of primary mullite (950–1150 °C), while the mullite/spinel ratio and mullite crystallite size make reliable thermal markers in the domain of secondary mullite (1100–1200 °C), thus covering a wide range of temperature likely to be used in traditional earthenware making.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107582"},"PeriodicalIF":5.3,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142323854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elden Willems , Niels Van Velthoven , Erik Smolders , Maarten Everaert
{"title":"One-pot synthesis of MgAl layered double hydroxides (LDH) from weathered tropical soils","authors":"Elden Willems , Niels Van Velthoven , Erik Smolders , Maarten Everaert","doi":"10.1016/j.clay.2024.107580","DOIUrl":"10.1016/j.clay.2024.107580","url":null,"abstract":"<div><div>Nutrient recycling is imperative for moving towards a circular economy. Layered double hydroxides (LDH) have been suggested as materials of interest for phosphorus (P) recycling, as they can selectively recover P from liquid waste streams and can be used as efficient P fertilisers in agriculture. Local P recycling with LDH can be particularly valuable for smallholder farmers with limited access to fertilisers, <em>e.g.</em> in tropical regions. However, conventional LDH production relies on external sources of Al<sup>3+</sup> for the synthesis of Mg<img>Al LDH. The present work proposed a new fertiliser technology based on LDH partly synthesized at room temperature with weathered soil as a local and omnipresent source of Al, supplemented with MgO and NaOH. The successful synthesis of LDH <em>via</em> this approach was confirmed by X-ray diffractometry (XRD). The capacity of this LDH to recover P was determined with synthetic P solutions and human urine as a waste model. A chemical desorption test demonstrated the available nature of P sorbed onto the soil-based LDH, which largely outperformed the availability of P sorbed onto the untreated soil. Finally, the fertiliser potential of the soil-based LDH loaded with recycled P was confirmed in a pot trial with rice (<em>Oryza sativa</em> L.) in weathered soil, indicating the combined P fertiliser and liming effect. Taken together, this study presented the proof-of-concept of a novel technology for local P recycling in tropical regions.</div></div>","PeriodicalId":245,"journal":{"name":"Applied Clay Science","volume":"261 ","pages":"Article 107580"},"PeriodicalIF":5.3,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}