Search Results (60)

“Miloschite”, a chromium-containing halloysite with intense blue hues, was first discovered in 1835 in Rudnjak, Serbia. Some of the collected “miloschite” samples remained in Serbia and are kept in the University Collection of Minerals and Rocks (Faculty of Mining and Geology, University of Belgrade) and in the Natural History Museum in Belgrade. During the 19th and 20th centuries, numerous studies examined this mineral. From the original samples collected at the type locality—initially described as “miloschite” and later confirmed to be varieties of halloysite enriched in chromium—subsequent interpretations of the authors on similar material from other localities worldwide led to a misinterpretation of “miloschite” as chromium-bearing kaolinite. This reinterpretation now requires revision. This investigation was carried out on an original sample employing techniques such as powder X-ray diffraction, thermal and various spectroscopic methods, along with assessments of cation exchange capacity, specific surface area, and color determination. Analyses reveal that “miloschite” primarily consists of chromium-bearing halloysite, where chromium is evenly distributed on the microscale and fills octahedral sites within the clay lattice. This research aims to reaffirm the status of “miloschite” as a significant geoheritage material from Serbia and to preserve its nomenclatural integrity as the chromium variety of halloysite. Full article

Medium and heavy rare earths (REEs) are mainly from weathered crust elution-deposited rare earth ores (WREOs), where REEs are adsorbed in ionic form on the surface of clay minerals such as kaolinite, illite, halloysite, etc. REEs in WREOs are extracted through the in situ leaching process with (NH₄)₂SO₄ solution via ion exchange. However, this process often results in the swelling of clay minerals, subsequently destroying the ore body structure and causing landslides. This study investigated the inhibitory effects of humic acid (HA) on the swelling of primary clay minerals. An optimal inhibition on the swelling of clay minerals was demonstrated at 0.2 g/L. HA was mixed with 0.1 mol/L (NH₄)₂SO₄ solution at the solution pH of 6.8 and temperature of 25 °C. The swelling efficiency of kaolinite, illite, and halloysite in presence of HA decreased by 0.29%, 1.19%, and 0.19%, respectively, compared to using (NH₄)₂SO₄ alone. The surface hydration parameter of clay minerals was further calculated through viscosity theory. It was demonstrated that the surface hydration parameter of kaolinite and halloysite decreased nearly threefold, while that of illite decreased fivefold, demonstrating a desirable inhibition on clay swelling with HA. Viscosity theory offers valuable theoretical support for the development of anti-swelling agents. Full article

As the production of electric vehicles grows, the rare earth elements Pr and Nd become increasingly significant, as they are key in magnetic materials production. In order to achieve the green and efficient recovery of Pr and Nd from the rare earth leachate, this paper selected kaolinite and halloysite as adsorbents to conduct rare earth solution adsorption experiments for exploring the effects of the initial leachate concentration, the solution pH, and the adsorption temperature on the adsorption process. The adsorption characteristics of Pr and Nd by clay minerals were analyzed by quantum chemical calculation. The results showed that the adsorption effects of clay minerals on Pr and Nd decreased with the rise of leachate concentration. When leachate pH increased, the adsorption efficiency of kaolinite and halloysite for Pr firstly increased and then decreased, and the optimal adsorption efficiency was 13.33% and 24.778% at pH 6, respectively. The adsorption effects of kaolinite and halloysite on Nd enhanced gradually with the increase in pH, which increased to 15.925% and 30.482% at pH 7, respectively. With temperature increased, the adsorption of Pr and Nd by kaolinite and halloysite was positively correlated. The isothermal adsorption model was fitted to the experimental data, and it was found that the adsorption of Pr and Nd by kaolinite and halloysite was consistent with the Langmuir model, with R² above 0.96, indicating that the adsorption process was a single molecular layer adsorption. The results provide theoretical support for the effective recycling of Pr and Nd, which is of great significance for the utilization of rare earth resources in permanent magnets. Full article

This study focused on creating a novel material by integrating ZnO and CuO nanoparticles into the structure of halloysite using a hydrothermal method. The formation of the nanocomposite was validated through X-ray diffraction and Raman analysis, which confirmed the presence of ZnO and CuO phases without compromising the structure of halloysite. Microscopic analysis revealed a well-distributed presence of metallic oxide nanoparticles within the nanotubular structure of halloysite, which adhered to both the outer and inner surfaces of the clay mineral. Optical characterization identified a substantial density of defects, which played a key role in improving the performance of the supported semiconductors. Furthermore, the narrow band gap at 3.02 eV promoted the mobility of photogenerated charges. Photocatalytic tests yielded promising results, demonstrating a synergistic effect between photocatalysis and adsorption processes that positively influenced the removal of ciprofloxacin from solutions. The material achieved up to 76% removal of the antibiotic within 120 min, utilizing a catalyst concentration of 0.5 g L⁻¹ with a pollutant concentration of 20 mg L⁻¹. In reuse experiments, the material exhibited high recyclability even after multiple reaction cycles. Halloysite-based nanocomposites represent a strategic advancement in environmental remediation technologies, contributing to the development of clean, effective, and reusable materials. Full article

Weathered crust elution-deposited rare earth ores (WCE-REOs) are the primary global source of medium and heavy rare earth elements (M/HREEs). The recent discovery of high-altitude (1500–2500 m) WCE-REOs in southern Yunnan Province, China, presents new opportunities for the development of M/HREE resources. This study investigates the enrichment and fractionation mechanisms of rare earth elements (REEs) in these deposits through a systematic analysis of three representative weathering profiles associated with the Lincang granite batholith. The analytical results indicate that the profiles consist mainly of clay minerals (kaolinite, halloysite, illite, minor montmorillonite) and iron oxides, with high SiO₂ (64.10–74.40 wt.%) and Al₂O₃ (15.50–20.20 wt.%) and low CaO/MgO—typical of weathered REE deposits. The total REE contents (238.12–1545.53 ppm) show distinct fractionation: LREE-enriched upper layers and HREE-enriched deeper zones. Sequential extraction revealed that the REEs in the Lincang granite weathering profiles predominantly occur in ion-exchangeable, residual, and iron-manganese oxide-bound states (>95% total REEs). Ion-exchangeable REEs showed depth-dependent enrichment (peaking at 819.96 ppm), while iron-manganese oxides exhibited a strong REE affinity (up to 47% total REEs), with amorphous phases that were preferentially enriched in Ce (partitioning >80%). Fissure systems exerted critical control over the redistribution of elements, particularly REEs. Full article

Sustainable strategies are required to mitigate elevated atmospheric CO₂ levels. Achieving that by adsorption, especially by using clay-based adsorbents, drew attention. These are even more promising when these adsorbents are obtained by low-cost modifications. This study evaluates the effect of ball milling on the carbon capture performance of Australian halloysite nanotube (HNT)-rich kaolin samples: one without iron impurities (Hal) and the other with iron impurities (HalFe). The iron was mainly nested within illite/mica minerals in HalFe. Samples were ball-milled for 30 and 60 min, and their CO₂ sorption was assessed at various pressures and temperatures. Crystallography, electronic microscopy, and surface area and charge characterization revealed reduced length and increased width of tubular structure following ball milling, leading to higher specific surface area without compromising crystallinity. CO₂ sorption of Hal increased 14% at 20 bar and 15 °C after 60 min milling, with a ~300% rise at near-atmospheric pressures. Conversely, milling negatively affected CO₂ sorption of HalFe, likely due to iron/illite-mica-related damage during milling. Crystallography, infrared, and thermographic analyses revealed physisorption as the primary sorption mechanism. Since direct disposal of CO₂-laden materials is against sustainability principles, these materials were tested for methylene blue removal from aqueous solutions, achieving ~83% (Hal) and ~91% (HalFe) removal efficiencies. This highlights HNTs-rich kaolin clays’ valorization potential for carbon capture and utilization (CCU). Full article

Synthetic alumosilicates are used in many industrial applications, and the synthesis of clay minerals under different conditions allows us to understand the conditions of their formation. This study examined the impact of varying silica precursors, pH conditions and synthesis durations. Synthetic kaolinite group mineral analogues were investigated by X-ray diffraction, scanning electron microscopy and infrared spectroscopy. Additionally, the crystallinity index was calculated. The impact of using different silica sources on the structural features of synthetic kaolinite group analogues was revealed. The use of a Nanosil precursor resulted in the formation of highly crystalline kaolinite. The most significant alterations in the course of synthesis were observed at different pH values. The formation of various synthetic analogues of minerals from the kaolinite group was observed: at a high pH, the formation of halloysite with a small admixture of kaolinite was observed. Conversely, the synthesis resulted in the formation of ordered kaolinite at a low pH. The crystallinity index of the resulting synthesized kaolinite analogues rises as the synthesis duration increases, while the quantity of non-crystallized material decreases. The changes in the crystallinity of kaolinite when using different silica precursors are related to the different homogenization of the material that occurs at the stage of alumosilica gel formation. Full article

Polymers of natural origin, such as representatives of various polysaccharides (e.g., cellulose, dextran, hyaluronic acid, gellan gum, etc.), and their derivatives, have a long tradition in biomedical applications. Among them, the use of chitosan as a safe, biocompatible, and environmentally friendly heteropolysaccharide has been particularly intensively researched over the last two decades. The potential of using chitosan for medical purposes is reflected in its unique cationic nature, viscosity-increasing and gel-forming ability, non-toxicity in living cells, antimicrobial activity, mucoadhesiveness, biodegradability, as well as the possibility of chemical modification. The intuitive use of clay minerals in the treatment of superficial wounds has been known in traditional medicine for thousands of years. To improve efficacy and overcome the ubiquitous bacterial resistance, the beneficial properties of chitosan have been utilized for the preparation of chitosan–clay mineral bionanocomposites. The focus of this review is on composites containing chitosan with montmorillonite and halloysite as representatives of clay minerals. This review highlights the antibacterial efficacy of chitosan–clay mineral bionanocomposites in drug delivery and in the treatment of topical skin infections and wound healing. Finally, an overview of the preparation, characterization, and possible future perspectives related to the use of these advancing composites for biomedical applications is presented. Full article

This paper presents the results of borehole investigations and laboratory tests carried out to characterize the soils derived from in situ weathering of tuff in Central Java, Indonesia. The 70 m thick weathering profile of the Quaternary tuff consisted of residual soil and completely to highly decomposed rocks. The relatively low dry unit weight and cohesion but high water content, porosity, plastic and liquid limits, and angle of internal friction of the soils in the present study were related to the dominance of halloysite clay minerals. The established relationships to predict soil shear strength parameters from the soil plasticity index and standard penetration test (SPT) N-values were examined, and linear and non-linear relationships for soils derived from in situ weathering of tuff were proposed. Full article

Recently, fluorescent sensors have gained considerable attention due to their high sensitivity, low cost and noninvasiveness. Among the different materials that can be used for this purpose, carbon dots (CDs) represent valuable candidates for applications in sensing. These, indeed, are easily synthesized, show high quantum yield and are highly biocompatible. However, it was pointed out that the photoluminescence properties of these nanomaterials are strictly dependent on the synthetic and purification methods adopted. The presence of halloysite nanotubes (HNTs), a natural, low cost and biocompatible clay mineral, has been found to be efficient in obtaining small and highly monodispersed CDs without long and tedious purification techniques. Herein, we report the comparison of synthetic pathways for obtaining halloysite-N-doped CDs (HNTs-NCDs) that could be used in biological sensing. One was based on the synthesis of N-doped CDs by a bottom-up approach on HNTs’ surface by a MW pyrolysis process; the other one was based on the post-modification of pristine N-doped CDs with halloysite derivatives. The evaluation of the best synthetic route was performed by different physico-chemical techniques. It was found that the bottom-up approach led to the formation of N-doped CDs with different functional groups onto the HNTs’ surface. This evidence was also translated in the different fluorescence quantum yields and the existence of several functional groups in the obtained materials was investigated by potentiometric titrations. Furthermore, the ability of the synthesized nanomaterials as sensors for Fe³⁺ ions detection was assessed by spectroscopic measurements, and the cellular uptake was verified by confocal/fluorescence microscopies as well. Full article

Aqueous complexation has long been considered the only viable means of transporting gold to depositional sites in hydrothermal ore-forming systems. Here, we present direct evidence supporting an alternative hypothesis, namely, the transport of gold as colloidal particles. We observed nano-scale gold particles adsorbed on halloysite and micro-scale gold particles in altered rocks by TEM and SEM in the Shanggong orogenic gold deposit. Based on this evidence, we propose a feasible model for the origin of microscopic gold particles in alteration zones. In the early stage of ore-forming fluid, gold may migrate in the form of collaurum, which is maintained by supercritical CO₂ and colloidal silica. Low salinity and high pressure are conducive to the stable migration of colloidal gold. When the physicochemical conditions change, some collaurum is precipitated and adsorbed by the clay minerals produced by hydrothermal alteration, and some collaurum undergoes growth and evolves into micro-submicrometer-sized gold particles. This study highlighted the significance of collaurum in the formation of orogenic gold deposits. Full article

The use of aluminum-rich clays and bauxites as refractory materials is common. Upon firing, these materials form mullite crystals in the shape of needles embedded in a siliceous and vitreous matrix, with mullite being responsible for the refractory properties. In this study, bauxite samples for use in refractory applications have been characterized. Chemical analysis revealed that the alumina content varied between 34 and 40%, with silica values generally being high (around 40%), except for one sample (26%). Two samples were found to be the most suitable for use as “refractory clay” refractories. However, high silica or Fe oxide contents can affect mineralogical transformations at high temperatures. Mineralogical analysis confirmed the presence of several minerals in the bauxite materials, including kaolinite, halloysite, anatase, rutile, gibbsite and boehmite. Differential thermal analysis (DTA) showed the decomposition of gibbsite and its partial transformation to boehmite and alumina, and the dehydroxylation of kaolinite, with primary mullite crystallization observed at a high temperature. These findings provide valuable information for the selection and optimization of bauxite materials for refractory applications, considering their chemical composition and mineralogical characteristics. Full article

In recent years, the coagulation properties of inorganic minerals such as kaolin and zeolite have been demonstrated. This study aimed to assess the hemostatic properties of three local clays from China: natural kaolin from Hainan, natural halloysite from Yunnan, and zeolite synthesized by our group. The physical and chemical properties, blood coagulation performance, and cell biocompatibility of the three materials were tested. The studied materials were characterized by using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). All three clays showed different morphologies and particle size, and exhibited negative potentials between pH 6 and 8. The TGA and DSC curves for kaolin and halloysite were highly similar. Kaolin showed the highest water absorption capacity (approximately 93.8% ± 0.8%). All three clays were noncytotoxic toward L929 mouse fibroblasts. Kaolin and halloysite showed blood coagulation effects similar to that exhibited by zeolite, indicating that kaolin and halloysite are promising alternative hemostatic materials. Full article

Currently, the primary method for leaching rare earth ores is through in situ leaching. This approach involves contact between clay minerals and liquids, which can lead to the potential swelling of clay minerals with water, triggering natural disasters such as landslides. The main purpose of this study is to select the suitable anti-swelling solution for Hunan Jianghua ionic rare earth ore. According to the ore composition analysis, 88 wt% of Hunan Jianghua ionic rare earth ore is composed of halloysite clay mineral. Therefore, halloysite clay mineral is used to investigate its anti-swelling behavior in order to provide a reference for future research on the selection of raw ore swelling inhibitors. In this study, the traditional leaching agent, MgSO₄ solution, was used as the solvent along with two additional compounds, CH₃COOK and KCl, which were prepared in different concentrations to form a new composite swelling inhibitor solution to observe their effect on the swelling rate of halloysite clay mineral. At the same time, the seepage velocity of halloysite clay mineral with different anti-swelling solutions is studied. The results indicate that the optimal concentration in the CH₃COOK + MgSO₄ solution system is 0.05 mol/dm³. At this concentration, the swelling rate is 5.129%, the inhibition rate is 20.08%, and the seepage velocity rate is 12.51 × 10⁻³ cm/min, respectively. In KCl + MgSO₄ solution, the swelling rate is 4.868%, the inhibition rate is 24.15% and the seepage velocity rate is 13.23 × 10⁻³ cm/min at the concentration of 0.02 mol/dm³, which is the optimum concentration. In addition, FTIR and TG studies have further demonstrated the mechanism by which these two composite bulking inhibitors inhibit the swelling of halloysite clay mineral. Full article

In order to reveal the influence of ammonium salts on the rare earth leaching process of weathered crust elution-deposited rare earth ores, ammonium acetate, ammonium chloride, and ammonium sulfate were used as leaching agents. The effects of the leaching agent on the rare earth leaching efficiency and the expansion, dissolution, and transformation behavior of clay minerals in the rare earth leaching process were studied. The results showed that rare earth leaching efficiency followed the order ammonium acetate > ammonium chloride > ammonium sulfate, with values of 90.60%, 85.96%, and 84.12%, respectively. The swelling ratio of clay mineral followed the order ammonium acetate < ammonium chloride < ammonium sulfate; the clay mineral swelling ratio was 2.09% when ammonium acetate was the leaching agent. Thermogravimetric analysis showed that the interlayer water content was the lowest when ammonium acetate was used as the leaching agent. Under the conditions of different leaching agents, the clay mineral contents changed from illite and halloysite to smectite and kaolinite. When ammonium acetate was used as the leaching agent, the relative conversion of illite was 1.49%, and that of smectite was only 0.17%. SEM analysis showed that the clay minerals expanded and dissolved obviously when ammonium chloride and ammonium sulfate were used as the leaching agents. Meanwhile, the clay mineral layered structure was relatively complete when ammonium acetate was used as the leaching agent. Therefore, when ammonium acetate was used as the leaching agent, it had the least effect on the swelling, dissolution, and transformation of clay minerals. This can provide a theoretical basis for the safe production of weathered crust elution-deposited rare earth ore, and for the screening of green and efficient leaching agents. Full article