Applied Clay Science最新文献_第4页

Functionalized montmorillonite clay with histidine for phosphate capture and recovery from wastewater sludge: Sustainable application as fertilizer to improve soil properties 含组氨酸的功能化蒙脱土用于污水污泥的磷酸盐捕获和回收：可持续用作肥料以改善土壤性质

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-20 DOI: 10.1016/j.clay.2025.108093

Mehr Un Nisa , Asim Yaqub , Tayyab Iqbal , Ali Turab Jafry , Huma Ajab

High phosphate discharge into water bodies causes eutrophication, leading to significant ecological harm. In the current study, we use L-His immobilized montmorillonite (His-MMt) adsorbents for the selective capturing of phosphate ions from aqueous solutions. The synthesized adsorbents were characterized through XRD, SEM, FTIR, and BET techniques. The intercalation of His-MMt interlayer exhibited an increase in surface area and active sites for phosphate adsorption, as demonstrated by the characterization study. The best adsorption conditions were found to at contact time = 30 min, pH = 4, phosphate concentration = 10 mg/L, adsorbent dosage = 20 mg, and temperature = 320 K. Kinetic studies revealed that the adsorption followed a pseudo-second-order model (R² ≥ 0.98). Equilibrium data followed the Freundlich isotherm model (R² ≥ 0.98), indicating multilayer adsorption. Thermodynamic analysis brings in ΔH° = 42.92 kJ/mol, ΔS° = 222.56 J/mol·K, and negative ΔG° values, endorsing an endothermic and spontaneous process with high entropy at the solid/solution interface. The maximum adsorption capacity was 81.96 mg/g, and the adsorbent maintained 79 % efficiency even after five regeneration cycles. About 85.1 % phosphate removal in sludge water was achieved as compared to 95 % in controlled experiments, demonstrating significant potential for practical use. Moreover, the phosphate-adsorbed His-MMt shown potential for commercial utilization as a fertilizer by eliminating secondary environmental effects.

高磷排入水体引起水体富营养化，造成重大生态危害。在目前的研究中，我们使用L-His固定化蒙脱土（His-MMt）吸附剂选择性地从水溶液中捕获磷酸盐离子。通过XRD、SEM、FTIR、BET等技术对合成的吸附剂进行了表征。表征研究表明，His-MMt夹层的插入增加了磷酸盐吸附的表面积和活性位点。最佳吸附条件为：接触时间30 min， pH = 4，磷酸盐浓度10 mg/L，吸附剂用量20 mg，温度320 K。动力学研究表明，吸附符合准二阶模型（R2≥0.98）。平衡数据符合Freundlich等温线模型（R2≥0.98），说明存在多层吸附。热力学分析得到ΔH°= 42.92 kJ/mol， ΔS°= 222.56 J/mol·K和负ΔG°值，表明这是一个在固/液界面具有高熵的吸热自发过程。最大吸附量为81.96 mg/g， 5次再生后吸附剂仍保持79%的吸附剂效率。与对照实验中95%的磷酸盐去除率相比，污泥水中的磷酸盐去除率约为85.1%，显示出实际应用的巨大潜力。此外，磷酸盐吸附的His-MMt通过消除二次环境影响而显示出作为肥料的商业利用潜力。

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引用次数: 0

Clay minerals in methane seep sediments of the Laptev Sea (Arctic): diagenetic transformations and buffering functions 北极拉普捷夫海甲烷渗漏沉积物中的粘土矿物：成岩转化与缓冲作用

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-17 DOI: 10.1016/j.clay.2025.108092

Maxim Rudmin , Alexey Ruban , Elena Deeva , Ivan Khitrin

This study first investigates diagenetic transformations and buffering functions of clay minerals in methane seep sediments from the Laptev Sea shelf (Arctic Ocean). Compared to background sediments, the seep-associated clays show enrichment in smectite content (up to 5.8 % vs. 0.8 %), attributed to reverse weathering, authigenic formation, and stabilization of smectite phases under reducing conditions. Illite group minerals in seep samples exhibit higher crystallinity and elevated Fe and Mg content in the octahedral sheets, likely reflecting the microbially mediated reduction of structural Fe³⁺. Chlorite is reduced by 2–6 wt% in seep sediments, reflecting partial dissolution and Fe²⁺ transfer into authigenic Fe-rich smectite. Submicron-sized pyrite crystals were detected on clay surfaces, indicating active sulfide diagenesis. TG-DCS-MS analyses revealed the unique buffering behavior of these clay minerals, as evidenced by their ability to sorb and release methane, water, CO₂, and sulfur-bearing gases. The release of methane above 400 °C directly indicates its physicochemical association with the clay matrix. The sustained NO⁺ emission (m/z = 30) above 700 °C is proposed as a novel diagnostic signal of seep-related diagenetic alteration. This is the first detailed characterization of diagenetic clay transformations in Arctic methane seep environments. These findings demonstrate that clay minerals in Arctic seep environments act as mineralogical proxies of the mobility of hydrocarbon gases. Their compositional and structural modifications provide critical insights into methane cycling and diagenetic pathways in Arctic marine sediments. The results promise to refine reconstructions of fluid migration history and the geochemical evolution of sedimentary basins influenced by methane seepage.

本研究首先探讨了北冰洋拉普捷夫海陆架甲烷渗漏沉积物中粘土矿物的成岩转化和缓冲作用。与背景沉积物相比，与渗漏相关的粘土显示出蒙脱石含量的富集（高达5.8%比0.8%），这归因于反向风化、自生形成和还原条件下蒙脱石相的稳定。渗漏样品中的伊利石族矿物结晶度较高，八面体薄片中Fe和Mg含量升高，可能反映了微生物介导的结构Fe3+还原。在深层沉积物中，绿泥石被还原2-6 wt%，反映了部分溶解和Fe2+向自生富铁蒙脱石的转移。在粘土表面检测到亚微米大小的黄铁矿晶体，表明硫化物成岩作用活跃。TG-DCS-MS分析揭示了这些粘土矿物独特的缓冲行为，证明了它们吸收和释放甲烷、水、二氧化碳和含硫气体的能力。400℃以上甲烷的释放直接表明其与粘土基质的物理化学关联。在700°C以上，持续的NO+发射（m/z = 30）被认为是与渗漏相关的成岩蚀变的新的诊断信号。这是北极甲烷渗漏环境中成岩粘土转化的首次详细表征。这些发现表明，北极渗漏环境中的粘土矿物可作为烃类气体流动性的矿物学指标。它们的组成和结构变化为北极海洋沉积物中的甲烷循环和成岩途径提供了重要的见解。研究结果有望为甲烷渗流影响下的沉积盆地流体运移史和地球化学演化的重建提供新的思路。

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引用次数: 0

Interparticle diffusion of dye cations in saponite dispersions monitored by fluorescence spectroscopy 荧光光谱法监测皂土分散体中染料阳离子的颗粒间扩散

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-17 DOI: 10.1016/j.clay.2025.108091

Juraj Krajč , Peter Boháč , Juraj Bujdák

For the first time, the interparticle diffusion of organic dye cations in hybrid clay colloids has been investigated in detail. The phenomenon was directly proven by experiments. Distances between dye molecules were monitored by Förster resonance energy transfer (FRET), enabling a sensitive probe of diffusion dynamics. Kinetic profiles demonstrated a strong temperature dependence, while additional effects such as concentration quenching and colloidal destabilization also contributed to the observed behavior. This methodology offers a powerful new route for characterizing diffusion phenomena in hybrid clay colloids and analogous systems.

首次详细研究了有机染料阳离子在杂化粘土胶体中的颗粒间扩散。实验直接证明了这一现象。染料分子之间的距离监测Förster共振能量转移（FRET），使扩散动力学的敏感探针。动力学曲线显示出强烈的温度依赖性，而额外的影响，如浓度猝灭和胶体不稳定也有助于观察到的行为。该方法为表征混合粘土胶体和类似体系中的扩散现象提供了一条强有力的新途径。

引用次数: 0

Modeling of zeolite 4A synthesis with different particle morphology from kaolin via response surface methodology 响应面法模拟高岭土合成不同颗粒形态4A沸石

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-16 DOI: 10.1016/j.clay.2025.108089

Ivan M. Zdretsov, Andrey M. Gerasimov

Zeolite 4A has numerous established and advanced applications. Using kaolin instead of conventional SiO₂ and Al₂O₃ sources makes its synthesis relatively green and low-cost. The best performance requires zeolite 4A to have high purity and specific particle size and morphology. However, fine-tuning these parameters is challenging due to the many influencing factors, and kaolin as a raw material only increases their number. Here, we modeled the dependence of zeolite 4A properties (relative crystallinity, yield, water vapor capacity, average size of particles and zeolite 4A cubic crystals, average number of cubes in agglomerate) on four synthesis parameters (temperature, time, stirring speed, Na₂O: Al₂O₃) via response surface methodology (RSM), namely the Box-Behnken design (BBD). Products were synthesized in two steps: metakaolinization and hydrothermal crystallization. We applied powder X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy with energy dispersive X-ray (SEM-EDX), differential thermal and thermogravimetric analysis (DTA-TGA), laser diffraction analysis (LDA) and other techniques to characterize the samples. As a result, we obtained response surfaces and used them to synthesize zeolite 4A with high relative crystallinity. In addition, it was found that at a high alkali content in the reaction mixture, e.g. Na₂O: Al₂O₃ = 5, the product particles are identical in shape to precursor ones but consist of tiny zeolite crystals with an average size of 0.94–1.83 μm. We also observed several previously known crystallization mechanisms. The obtained models, observations, and experimental data expand the toolbox for producing zeolites from kaolin, and may become the basis for relatively green and low-cost technology.

沸石4A有许多成熟和先进的应用。使用高岭土代替传统的SiO2和Al2O3源，使其合成相对绿色和低成本。最佳性能要求4A沸石具有较高的纯度和特定的粒度和形态。然而，由于影响这些参数的因素很多，对这些参数进行微调是具有挑战性的，而高岭土作为原材料只会增加它们的数量。在这里，我们通过响应面法（RSM），即Box-Behnken设计（BBD），模拟了沸石4A性质（相对结晶度、产率、水蒸气容量、颗粒和沸石4A立方晶体的平均尺寸、团聚体的平均立方体数）对四个合成参数（温度、时间、搅拌速度、Na2O: Al2O3）的依赖关系。产物的合成分为偏高岭土化和水热结晶两步。采用粉末x射线衍射（XRD）、x射线荧光光谱（XRF）、扫描电子显微镜与能量色散x射线（SEM-EDX）、差热与热重分析（DTA-TGA）、激光衍射分析（LDA）等技术对样品进行表征。得到了响应面，并用其合成了相对结晶度高的4A沸石。此外，在高碱含量的反应混合物中，如Na2O: Al2O3 = 5，产物颗粒形状与前驱体相同，但由平均尺寸为0.94 ~ 1.83 μm的微小沸石晶体组成。我们还观察到一些以前已知的结晶机制。所获得的模型、观察和实验数据扩展了从高岭土生产沸石的工具箱，并可能成为相对绿色和低成本技术的基础。

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引用次数: 0

Synthesis of modified illite coated with melamine and aminotrimethylene phosphonic acid and study on its flame-retardant properties for epoxy resin 三聚氰胺和氨基三亚甲基膦酸包覆改性伊利石的合成及其对环氧树脂的阻燃性能研究

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-15 DOI: 10.1016/j.clay.2025.108090

Weihua Meng , Da Yang , Shengnan Wang , Chenyang Liu , Pengyang Zou , Yuan Li , Jixing Xie , Jianzhong Xu

Epoxy resin (EP) is a high-performance polymer whose broader application is restricted by inherent flammability. In this work, a novel core-shell ILA@ATMEL was synthesized by coating natural illite with melamine-based aminotrimethylene phosphonate (ATMEL). The resulting hybrid was incorporated into EP to simultaneously improve flame retardancy and mechanical properties. With the addition of 9 phr ILA@ATMEL, the limiting oxygen index of EP composite reached 28.8 %, and the char residue at 800 °C increased from 17.82 % to 29.57 %. Cone calorimetry tests revealed notable reductions in peak heat release rate (33.57 %), total heat release (20.89 %), peak smoke production rate (29.37 %), and total smoke production (14.17 %) compared to those of pore EP. These improvements are attributed to synergistic flame-retardant mechanisms both in the condensed phase and the gas phase with Si, Al, P, and N elements. Moreover, ILA@ATMEL acts as a reinforcing filler at low loadings. The composite with 3 phr additive exhibited increases in elongation at break and tensile strength by 10.57 % and 18.86 %, respectively. This study demonstrates a feasible strategy for designing eco-friendly, high-performance EP composites with enhanced fire safety and mechanical durability via mineral-based core-shell flame retardants.

环氧树脂（EP）是一种高性能聚合物，但其固有的可燃性限制了其广泛应用。本文以三聚氰胺基氨基三亚甲基膦酸盐（ATMEL）包覆天然伊利石，合成了一种新型核壳ILA@ATMEL。将得到的混合物掺入EP中，同时提高了阻燃性和力学性能。添加9 phr ILA@ATMEL后，EP复合材料的极限氧指数达到28.8%，800℃下的焦渣由17.82%提高到29.57%。锥量热测试显示，与孔隙EP相比，峰值放热率（33.57%）、总放热率（20.89%）、峰值产烟率（29.37%）和总产烟率（14.17%）显著降低。这些改进归因于Si， Al， P和N元素在凝聚相和气相中的协同阻燃机制。此外，ILA@ATMEL在低负荷下充当补强填料。添加3phr的复合材料的断裂伸长率和抗拉强度分别提高了10.57%和18.86%。本研究展示了一种可行的策略，通过矿物基核壳阻燃剂来设计具有增强防火安全性和机械耐久性的环保、高性能EP复合材料。

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引用次数: 0

Layered zinc hydroxide–dipeptide hybrid integrated into silk-based 3D scaffolds aiming for biomedical applications 层状氢氧化锌-二肽杂化物集成到丝基3D支架中，旨在用于生物医学应用

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-12 DOI: 10.1016/j.clay.2025.108087

Denise Eulálio , Mariana Pires Figueiredo , Simone S. Silva , Luísa C. Rodrigues , Emanuel M. Fernandes , Albino Martins , Albina Franco , Diana Soares da Costa , Richard Landers , Fabrice Leroux , Christine Taviot-Gueho , Dalva Lúcia Araújo de Faria , Rui L. Reis , Vera Regina Leopoldo Constantino

Zinc ions and N-acetylcysteine (NAC) are bioactive agents with key physiological roles. When associated with biomacromolecules such as silk fibroin (SF), they offer a promising pathway for advanced biomedical applications. This study reports the synthesis of layered zinc hydroxide (LZH) intercalated with NAC as well as the development of LZH-NAC/SF scaffolds. The synthesis of LZH-NAC was conducted using a constant-pH method, and experimental parameters were controlled to obtain a monophasic LZH. Comprehensive structural, spectroscopic, textural, and thermal characterisation confirmed the successful intercalation of NAC into the LZH. The employed methodology enabled the production of an LZH-NAC nanomaterial with an encapsulation efficiency of approximately 80 % by mass and a loading capacity of around 30 %. To evaluate its biomedical potential, LZH-NAC/SF 3D composite scaffolds were prepared by dispersing LZH-NAC in SF solution, followed by freezing and freeze-drying. The average pore sizes observed in the scaffolds ranged from 75 to 87 μm, and the swelling capacity was approximately 1700 % after incubation in phosphate-buffered saline (pH 7.4). Cytocompatibility assays revealed that LZH-NAC/SF scaffolds supported cell viability at a zinc concentration of 0.189 mg/mL, similar to that of the SF and NAC/SF scaffolds. These results underscore the potential of LZH-NAC/SF scaffolds as multifunctional biomaterials for the controlled delivery of therapeutic agents, with significant implications for tissue engineering and drug delivery systems.

锌离子和n -乙酰半胱氨酸（NAC）是具有重要生理作用的生物活性物质。当与生物大分子如丝素蛋白（SF）相结合时，它们为先进的生物医学应用提供了一条有希望的途径。本研究报道了层状氢氧化锌（LZH）嵌入NAC的合成及LZH-NAC/SF支架的研制。采用恒ph法合成LZH- nac，并对实验参数进行控制，得到单相LZH。综合结构、光谱、织构和热表征证实了NAC成功嵌入LZH。所采用的方法能够生产出LZH-NAC纳米材料，其包封效率约为80%，负载能力约为30%。为了评估其生物医学潜力，我们将LZH-NAC分散在SF溶液中，然后进行冷冻和冷冻干燥，制备LZH-NAC/SF 3D复合支架。在磷酸盐缓冲盐水（pH 7.4）中孵育后，支架的平均孔径为75 ~ 87 μm，膨胀容量约为1700%。细胞相容性实验表明，在锌浓度为0.189 mg/mL时，LZH-NAC/SF支架支持细胞活力，与SF和NAC/SF支架相似。这些结果强调了LZH-NAC/SF支架作为治疗药物控制递送的多功能生物材料的潜力，对组织工程和药物递送系统具有重要意义。

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引用次数: 0

Retrospective of chrysotile synthesis: From tough geoinspired process up to soft chemical design 温石棉合成回顾：从坚硬的土工工艺到柔软的化学设计

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-12 DOI: 10.1016/j.clay.2025.108088

Andrea Bloise , Ilaria Fuoco , Carmine Apollaro , Giovanni Vespasiano , Ekaterina Khrapova , Andrei Krasilin

Chrysotile, the fibrous form of serpentine, is characterized by the chemical formula Mg₃Si₂O₅(OH)₄. Over the past seventy years, significant research has focused on synthesizing chrysotile, initially for petrological studies and more recently for applications in nanotechnology, particularly high-purity chrysotile nanotubes and doped variants. Common synthesis methods involve hydrothermal reactions using cristobalite and periclase or magnesium hydroxide and silica gel mixtures. Most frequently used synthesis conditions generally include temperatures between 200 °C and 400 °C and pressures from 0.5 to 100 MPa, though these often result in impure chrysotile with unwanted phases. Despite the promise of doped chrysotile, natural fibers are often unsuitable for nanoscience due to foreign ions and mineral intergrowths. Recent studies explore the potential for creating isomorphic series as Mg₃Si₂O₅(OH)₄ – Ni₃Si₂O₅(OH)₄ or Mg₃Si₂O₅(OH)₄ - (Fe²⁺, Fe³⁺)_3-2Si₂O₅(OH)₄, examining the impact of nickel and iron on chrysotile's properties. This study provides a review of the reported synthesis methods for chrysotile, emphasizing the synthesis techniques, precursor materials, and the resulting crystal chemistry. The findings highlight the dynamic nature of chrysotile synthesis research, with implications for materials science, including the development of novel nanostructures and environmental remediation technologies.

温石棉是蛇纹石的纤维状结构，其化学特征为：Mg3Si2O5(OH)4。在过去的七十年里，重要的研究集中在温石棉的合成上，最初用于岩石学研究，最近用于纳米技术的应用，特别是高纯度的温石棉纳米管和掺杂变体。常用的合成方法包括用方英石和方长石或氢氧化镁和硅胶混合物进行水热反应。最常用的合成条件通常包括温度在200°C到400°C之间，压力在0.5到100 MPa之间，尽管这些条件通常会导致含有不需要相的不纯温石棉。尽管掺温石棉很有前途，但由于外来离子和矿物的共生，天然纤维往往不适合用于纳米科学。最近的研究探索了创建Mg3Si2O5(OH)4 - Ni3Si2O5(OH)4或Mg3Si2O5(OH)4 - (Fe2+, Fe3+)3-2Si2O5(OH)4等同构系列的潜力，研究了镍和铁对温sotile性能的影响。本文综述了温石棉的合成方法，重点介绍了合成技术、前驱体材料和所得晶体化学性质。这些发现突出了温石棉合成研究的动态性质，对材料科学，包括新型纳米结构和环境修复技术的发展具有重要意义。

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引用次数: 0

Five-year thermo-hydro-mechanical and chemical evolution of compacted bentonite: reactive transport 五年压实膨润土的热-水-力学和化学演化：反应性输运

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-10 DOI: 10.1016/j.clay.2025.108086

María Victoria Villar , Andrés Idiart , Emilie Coene , Jaime Cuevas , Ana María Melón , Ana I. Ruiz , Almudena Ortega , Ville Heino

To help describing and understanding the mechanisms and factors governing the geochemical evolution and mineralogical alteration of compacted bentonite under hydraulic and thermal gradients similar to those experienced by engineered barriers in radioactive waste repositories, an experimental and modelling programme was carried out. Six thermo-hydraulic tests were performed in cylindrical cells (10 × 10 cm) using compacted Wyoming-type bentonite. The bottom of the cells was initially heated at 90 °C and once hydraulic equilibrium was reached, hydration of the bentonite started through the top surface for different periods of time (1, 2.5 and 5 years). The top surface was maintained at 20 °C during the whole test duration to induce a thermal gradient. The composition of the hydration water reproduced, for half of the cells, that of a saline groundwater and for the other half, of a dilute glacial water. The temperature of the heater was increased to 110 °C after ∼1 year of hydration. At termination, the bentonite was characterised. The thermo-hydraulic evolution during operation, final state of the bentonite and its mineralogical changes were simulated with a thermo-hydro-chemical model and reported in a companion paper.

Hydration brought about dissolution of calcite and gypsum, partial substitution of exchangeable sodium by calcium in the interlayer and transport of solutes towards hotter areas, where they precipitated as anhydrite and halite when saline water was used. In the longer term, the concentration gradient prompted the diffusive transport of chloride. The cation exchange capacity did not change over time, confirming the lack of changes in the montmorillonite crystal-chemistry that the mineralogical analyses had shown. The smectite interlayer composition kept its predominant monovalent character, although the exchangeable magnesium and potassium increased transitorily towards the heater while the bentonite remained unsaturated. The patterns observed were the same irrespective of the kind of water used, but the processes were enhanced with saline water.

为了帮助描述和理解控制压实膨润土在水力和热梯度下的地球化学演化和矿物学变化的机制和因素，类似于放射性废物处置库中工程屏障所经历的情况，开展了一项实验和建模计划。采用压实的怀俄明型膨润土在圆柱形池（10 × 10 cm）中进行了6次热水力试验。细胞底部最初在90°C下加热，一旦达到水力平衡，膨润土的水化作用开始通过顶部表面，持续不同的时间（1年、2.5年和5年）。在整个测试期间，顶部表面保持在20°C，以诱导热梯度。水合水的成分，对一半的细胞来说，是盐水的地下水，对另一半来说，是稀释的冰川水。在水化1年后，加热器的温度升高到110°C。终止时，对膨润土进行了表征。利用热-水-化学模型模拟了膨润土运行过程中的热-水演化过程、膨润土的最终状态及其矿物学变化，并在相应的论文中报道。水合作用导致方解石和石膏溶解，层间钙部分取代了可交换性钠，溶质向较热的地区迁移，当使用盐水时，溶质以硬石膏和盐石的形式沉淀。长期来看，浓度梯度促进了氯离子的扩散输运。阳离子交换容量没有随着时间的推移而改变，证实了矿物学分析所显示的蒙脱土晶体化学没有变化。蒙脱石层间组成保持了其主要的单价特征，但可交换性镁和钾向加热器短暂增加，而膨润土仍保持不饱和。无论使用哪种水，观察到的模式都是相同的，但盐水增强了这一过程。

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引用次数: 0

Quarry waste clays as supplementary cementitious materials: Mineralogical evolution and pozzolanic performance after thermal activation 作为补充胶凝材料的采石场废粘土：热活化后的矿物学演化和火山灰性能

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-06 DOI: 10.1016/j.clay.2025.108085

Erdi Avci , Elif Sidimi , Nana Asaam , Aysu Dag , Atiye Tugrul , Priyadharshini Perumal

This study investigates the potential of thermally activated quarry waste as alternative supplementary cementitious materials (SCMs) for sustainable binder systems. Three clay-rich materials were collected from a sand quarry located on the European side of Istanbul: two natural overburden clays (Yellow Layer-YL and Blue Layer-BL) and one process-derived sludge waste (TA) generated during sand washing. All samples were sieved (<150 μm), dried, and calcined at 800 °C for 2 h. Mineralogical (XRD), chemical (XRF), and thermal (TG, FTIR) analyses were conducted to evaluate phase transformation and amorphous phase development. Pozzolanic reactivity was assessed by the R³ test, including heat release and bound water measurements. Results showed that the TA sample exhibited the highest reactivity due to its kaolinite content and fine, homogeneous particle structure. In contrast, the BL sample demonstrated limited reactivity owing to the dominance of thermally stable phases such as muscovite and albite. Mortar specimens prepared with 20 % SCM replacement were tested for compressive strength at 7, 14, and 28 days using both CEM I and CEM II binders. The TA-C mixture achieved a compressive strength index (CSI) of 102.9 % with CEM I at 14 days, indicating strong early-age performance, while YL-C showed the highest 28-day strength with CEM II (CSI = 97.9 %). These findings confirm that sludge-based SCMs, when properly activated, can match or even exceed the performance of conventional systems, offering a viable strategy for resource-efficient and low-carbon cementitious materials.

本研究探讨了热活化采石场废物作为可持续粘合剂系统替代补充胶凝材料（scm）的潜力。从位于伊斯坦布尔欧洲一侧的采石场收集了三种富含粘土的材料：两种天然覆盖层粘土（黄色层- yl和蓝色层- bl）和一种在洗砂过程中产生的工艺污泥废物（TA）。所有样品经过筛分（<150 μm），干燥，并在800°C下煅烧2小时。进行矿物（XRD），化学（XRF）和热（TG， FTIR）分析以评估相变和非晶相的发展。通过R3测试评估火山灰的反应性，包括热量释放和结合水测量。结果表明，TA样品高岭石含量高，颗粒结构细小均匀，反应活性最高。相比之下，由于白云母和钠长石等热稳定相的优势，BL样品表现出有限的反应性。使用CEM I和CEM II粘结剂，在7、14和28天测试用20% SCM替代的砂浆试件的抗压强度。TA-C混合物的抗压强度指数（CSI）在14天达到102.9%，显示出较强的早期性能，而YL-C混合物在28天的抗压强度最高（CSI = 97.9%）。这些研究结果证实，当适当激活时，基于污泥的SCMs可以匹配甚至超过传统系统的性能，为资源高效和低碳胶凝材料提供了可行的策略。

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引用次数: 0

Essential oil-loaded amine-modified HNTs composites for sustained release and enhanced antibacterial performance in root rot control 精油载胺改性HNTs复合材料缓释及增强根腐病防治抗菌性能

IF 5.8 2区地球科学 Q2 CHEMISTRY, PHYSICAL

Applied Clay Science

Pub Date : 2025-12-05 DOI: 10.1016/j.clay.2025.108066

Guixiang Teng , Hui Yao , Hongyu Wang , Shuting Zhang , Yanzan Meng , Meng Zhao , Yan Yang , Chun Zhang

To mitigate the detrimental effects of root rot disease on Chinese herbal medicines, this study developed an environmentally friendly sustained-release antimicrobial system (CEO@HNTs-NH₂) based on clove essential oil (CEO) loaded onto amino-functionalized Halloysite nanotubes (HNTs-NH₂). Characterization results revealed that CEO@HNTs-NH₂ enhanced the thermal stability of CEO and significantly strengthened their interaction. Density Functional Theory (DFT) calculations demonstrated negative values for both the adsorption energy (−0.5772 eV) and interaction energy (−0.2117 eV) of CEO@HNTs-NH₂, providing molecular-level insights into the sustained-release mechanism. The release studies demonstrated a significantly low cumulative release of 21.20 ± 0.43 % over 10 days, exhibiting Fickian diffusion kinetics (R² = 0.99). This controlled release profile effectively mitigates the inherent volatility of CEO. Innovatively, we fabricated HAK clay tablets by compounding CEO@HNTs-NH₂ with Attapulgite and Kaolin—serving as structural supporter and coating agent, respectively—at an optimal 3:2:2 ratio. The tablet formulation conditions were optimized by Box-Behnken Design, yielding the optimal parameters: molding temperature of 30 °C, pressure of 0.86 MPa, and holding time of 32 min. Finally, the pot experiments demonstrated that HAK tablets significantly reduced the plant disease severity of Rehmannia by 59.8 % (Prevention group) and 32.2 % (Treatment group) compared to the Pathogenic group, confirming their potentially antimicrobial efficacy. In summary, this clay mineral nanocomposite system achieves controlled release through synergistic physico-chemical interactions, offering an innovative strategy for the application of clay minerals in sustainable agriculture.

为了减轻根腐病对中草药的有害影响，本研究开发了一种环境友好型缓释抗菌系统（CEO@HNTs-NH2），该系统基于丁香精油（CEO）负载在氨基功能化埃洛石纳米管（HNTs-NH2）上。表征结果表明CEO@HNTs-NH2增强了CEO的热稳定性，显著增强了它们之间的相互作用。密度泛函理论（DFT）计算表明CEO@HNTs-NH2的吸附能（- 0.5772 eV）和相互作用能（- 0.2117 eV）均为负值，为分子水平上的缓释机制提供了深入的了解。释放试验表明，10 d内的累积释放量为21.20±0.43%，符合菲克扩散动力学（R2 = 0.99）。这种受控的发布配置文件有效地减轻了CEO固有的不稳定性。我们创新地将CEO@HNTs-NH2与凹凸棒土和高岭土（分别作为结构载体和包衣剂）以3:2:2的最佳比例复配制成HAK粘土片。采用Box-Behnken设计法对片剂的处方条件进行优化，得到最佳工艺参数：成型温度30℃，压力0.86 MPa，保温时间32 min。最后，盆栽实验表明，与致病组相比，HAK片显著降低了地黄植物病害严重程度，分别降低了59.8%（预防组）和32.2%（治疗组），证实了其潜在的抗菌作用。综上所述，该黏土矿物纳米复合体系通过物理化学协同作用实现控释，为黏土矿物在可持续农业中的应用提供了一种创新策略。

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