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Most of the therapeutic systems developed for managing chronic skin wounds lack adequate mechanical and hydration properties, primarily because they rely on a single component. This study addresses this issue by combining organic and inorganic materials to obtain hybrid films with enhanced mechanical behavior, adhesion, and fluid absorption properties. To that aim, chitosan/hydrolyzed collagen blends were mixed with halloysite/antimicrobial nanohybrids at 10% and 20% (w/w) using glycerin or glycerin/polyethylene glycol-1500 as plasticizers. The films were characterized through the use of Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and electron microscopy. The mechanical properties were evaluated macroscopically using tensile tests, and at a nanoscale through atomic force microscopy (AFM) and nanoindentation. Thermodynamic studies were conducted to assess their hydrophilic or hydrophobic character. Additionally, in vitro cytocompatibility tests were performed on human keratinocytes. Results from FTIR, TGA, AFM and electron microscopy confirmed the hybrid nature of the films. Both tensile tests and nanomechanical measurements postulated that the nanohybrids improved the films’ toughness and adhesion and optimized the nanoindentation properties. All nanohybrid-loaded films were hydrophilic and non-cytotoxic, showcasing their potential for skin wound applications given their enhanced performance at the macro- and nanoscale.

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.

One solution to comply with the strict regulations of the European Commission and reduce the environmental footprint of composites is the use of composite materials based on bio-polymers and fillers from natural resources. The aim of our work was to obtain and analyze the properties of bio-polymer nanocomposites based on bio-PA (PA) and feather keratin–halloysite nanohybrid. Keratin (KC) was mixed with halloysite (H) as such or with the treated surface under dynamic conditions, resulting in two nanohybrids: KCHM and KCHE. The homogenization of PA with the two nanohybrids was conducted using the extrusion processing process. Two types of nanocomposites, PA–KCHM and PA–KCHE, with 5 wt.% KC and 1 wt.% H were obtained. The properties were analyzed using SEM, XRD, FTIR, RAMAN, TGA, DSC, tensile/impact tests, DMA, and nanomechanical tests. The best results were obtained for PA–KCHE due to the stronger interaction between the components and the uniform dispersion of the nanohybrid in the PA matrix. Improvements in the modulus of elasticity and of the surface hardness by approx. 75% and 30%, respectively, and the resistance to scratch were obtained. These results are promising and constitute a possible alternative to synthetic polymer composites for the automotive industry.

Chemical modification of the surface of halloysite nanotubes (HNT) by alkalization (with sodium hydroxide (NaOH)) and grafting with silanes (bis(trimethylsilyl)amine (HMDS)) was carried out. The efficiency of the alkalization and grafting process was evaluated by X–ray diffraction (XRD), Fourier–transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and the nitrogen adsorption method were used. XRD and FTIR analysis confirmed the formation of bonds of trimethylsilyl groups to the HNT surface which changed the nature of the surface from hydrophilic to hydrophobic. In addition, it was noted that grafting with silanes decreases by 7.2% the specific surface area of the halloysite compared to the alkalized material. High–density polyethylene (HDPE) composites with halloysite (HNT), alkalized halloysite (alk–HNT), and HMDS–modified halloysite (m–HNT) were processed in the molten state in a Brabender mixer chamber. On SEM/EDS micrographs of HDPE composites with silanized HNT, a change in surface characteristics from smooth to ductile was observed. Higher melting point values based on differential scanning calorimetry (DSC) analysis of HDPE composites with 5%wt silanized halloysite in comparison with HNT and alk–HNT of, respectively, 2.2% and 1.4% were found, which indicates a slight beneficial influence of the filler on the quality of ordering of the crystalline phase of the matrix.

The adsorption of copper ions and Reactive Red 120 azo dye (RR-120) as models of water pollutants on unmodified halloysite (H-NM), as well as halloysites modified with sulfuric acid (H-SA) and (3-aminopropyl)triethoxysilane (H-APTES), was investigated. The results showed that adsorption of both the adsorbates was pH-dependent and increased with the increase in halloysite dosage. The adsorption kinetics were evaluated and the results demonstrated that the adsorption followed the pseudo-second-order model. The adsorption isotherms of Cu(II) ions and RR-120 dye on the halloysites were described satisfactorily by the Langmuir model. The maximum adsorption capacities for the Cu(II) ions were 0.169, 0.236, and 0.507 mmol/g, respectively, for H-NM, H-SA, and H-APTES indicating that the NH2-functionalization rather than the surface area of the adsorbents was responsible for the enhanced adsorption. The adsorption capacities for RR-120 dye were found to be 9.64 μmol/g for H-NM, 75.76 μmol/g for H-SA, and 29.33 μmol/g for H-APTES. The results demonstrated that APTES-functionalization and sulfuric acid activation are promising modifications, and both modified halloysites have good application potential for heavy metals as well as for azo dye removal.

Despite the mechanical and physical properties of polyurethane foams (PUF), their application is still hindered by high inflammability. The elaboration of effective, low-cost, and environmentally friendly fire retardants remains a pressing issue that must be addressed. This work aims to show the feasibility of the successful application of natural nanomaterials, such as halloysite nanotubes and nanocellulose, as promising additives to the commercial halogen-free, fire-retardant triphenyl phosphate (TPP) to enhance the flame retardance of open-cell polyurethane foams. The nanocomposite foams were synthesized by in situ polymerization. Investigation of the mechanical properties of the nanocomposite PUF revealed that the nanoscale additives led to a notable decrease in the foam’s compressibility. The obtained results of the flammability tests clearly indicate that there is a prominent synergetic effect between the fire-retardant and the natural nanoscale additives. The nanocomposite foams containing a mixture of TPP (10 and 20 parts per hundred polyol by weight) and either 10 wt.% of nanocellulose or 20 wt.% of halloysite demonstrated the lowest burning rate without dripping and were rated as HB materials according to UL 94 classification.

Post-recycling sodium polyacrylate (SPA) derived from the selective recycling of personal hygiene products was tested as a potential key component of soil modifiers. Recycled SPA in combination with layered aluminosilicate (halloysite) with the sorption capacity of fertilizers allows for the creation of a fully functional, original system responsible for both water retention in soil and controlled dosing of fertilizers. The use of post-recycling SPA (possibly partially supplemented with virgin SPA) is advantageous for the natural environment. The results of different water types retention in post-recycling SPA (deionized water, rainwater, tap water) are discussed. The most beneficial effects of R-SPA swelling and water accumulation are achieved when it comes into contact with rainwater. The clear impact of Mg2+ ions on the sorption capacity of R-SPA introduces the need for a technological compromise between the solution composition (N, P, K or N, P, K, Mg) affecting its fertilization value and the possibility of obtaining maximum R-SPA swelling. The sorption capacity of R-SPA can be slightly increased by using R-SPA/V-SPA mixtures, but R-SPA still plays a decisive role in this system. The possibility of technological adjustment of the leaching rate of fertilizer components under dynamic conditions using different combinations of (R-SPA/V-SPA)/HAL was demonstrated by column tests.

The present paper describes the preparation and characterization of novel microbeads from alginate filled with nanoclay such as halloysite nanotubes (HNTs). HNTs were used as support for the growth of layered double hydroxide (LDH) crystals producing a flower-like structure (HNT@LDH). Such nanofiller was loaded with grapefruit seed oil (GO), an active compound with antimicrobial activity, up to 50% wt. For comparison, the beads were also loaded with HNT and LDH separately, and filled with the same amount of GO. The characterization of the filler was performed using XRD and ATR spectroscopy. The beads were analyzed through XRD, TGA, ATR and SEM. The functional properties of the beads, as nanocarriers of the active compound, were investigated using UV-vis spectroscopy. The release kinetics were recorded and modelled as a function of the structural characteristics of the nanofiller.

Chickpea flour is an affordable natural blend of starch, proteins, and lipids, which can create films with suitable properties as an eco-friendly packaging material. Nanoclays’ incorporation into natural biopolymers enhances the barrier properties of the resulting nanocomposites, so they could improve the properties of flour films. The objective of this work was to assess the influence of three types of nanoclays (halloysite, bentonite, and Cloisite 20A) at two concentrations on the characteristics of chickpea flour films. In general terms, when the lowest dose (5%) was added, no or very slight significant differences with the control were observed in most parameters, except for thermal stability and opacity, which increased, and solubility, which decreased. At the highest concentration (10%), films containing any of the nanoclays demonstrated greater thermal stability, opacity, and rigidity while being less soluble than those without nanofillers. Bentonite exhibited superior film structure distribution compared to other nanoclays. At the highest concentration, it had the most significant impact on modifying the properties of chickpea flour films, increasing their tensile and puncture strengths while decreasing elasticity and water vapor permeability. The incorporation of nanoclays into chickpea flour films could be a useful technique to enhance their properties.

Hydrogels are characterized by their property of absorbing and releasing a high content of water and water-based liquids; thus, they can be applied in agriculture as controlled-release water and fertilizer products. The focus of this research was efficient and low-cost natural polymer-based hydrogels obtained by crosslinking gellan gum (GGLA) and starch (ST) with acetic acid (CA) and loading them with either bentonite (BET) and/or halloysite (HAL). The hydrogels were obtained by mixing 100, 75, 50, 25, and 0 wt.% of GGLA with 0, 25, 50, 75, and 100 wt.% ST water solutions. To obtain the networks, they were crosslinked with 10, 5, and 2 wt.% of CA and loaded with 2, 5, and 10 wt.% of BET and/or HAL. The samples were analyzed by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), their swelling in water, and the state of bound water properties. The results of these analyses point to the formation of a polymeric network with a decomposition temperature of >250 °C, and tailorable swelling properties that vary between 3 and 77, depending on the hydrogel composition. In summary, GGLA-ST-BET/HAL hydrogels are a good option for eco-friendly agriculture materials.

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.

This study reports on the development of nanocomposites utilizing a mineral inhibitor and a micronutrient filler. The objective was to produce a slow release fertilizer, with zinc sulfate as the filler and halloysite nanotubes as the inhibitor. The study seeks to chemically activate the intercalation of zinc into the macro-, meso-, and micropores of the halloysite nanotubes to enhance their performance. As a result, we obtained three nanocomposites in zinc sulfate solution with concentrations of 2%, 20%, and 40%, respectively, which we named Hly-7Å-Zn2, Hly-7Å-Zn20, and Hly-7Å-Zn40. We investigated the encapsulation of zinc sulfate in halloysite nanotubes using X-ray diffraction analysis, transmission electron spectroscopy, infrared spectroscopy (FTIR), and scanning electron microscopy with an energy-dispersive spectrometer. No significant changes were observed in the initial mineral parameters when exposed to a zinc solution with a concentration of 2 mol%. It was proven that zinc was weakly intercalated in the micropore space of the halloysite through the increase in its interlayer distance from 7.2 to 7.4. With an increase in the concentration of the reacted solution, the average diameter of the nanotubes increased from 96 nm to 129 nm, indicating that the macropore space of the nanotubes, also known as the “site”, was filled. The activated nanocomposites exhibit a maximum fixed content of adsorbed zinc on the nanotube surface of 1.4 wt%. The TEM images reveal an opaque appearance in the middle section of the nanotubes. S SEM images revealed strong adhesion of halloysite nanotubes to plant tissues. This property guarantees prolonged retention of the fertilizer on the plant surface and its resistance to leaching through irrigation or rainwater. Surface spraying of halloysite nanotubes offers accurate delivery of zinc to plants and prevents soil and groundwater contamination, rendering this fertilizer ecologically sound. The suggested approach of activating halloysite with a zinc solution appears to be a possible route forward, with potential for the production of tailored fertilizers in the days ahead.

Porous phyllosilicate-based ceramics were manufactured by freeze-tape casting from clays of different particle size and morphology in order to characterize their microstructure and stress to rupture changes before and after firing. Three raw clays were selected: HCR (77% Halloysite–10Å), KORS (29% kaolinite), and KCR kaolin (98% kaolinite). These clays exhibited a monomodal distribution and were used to prepare four slurries, three with each clay material and one consisting of a mixture of KCR and HCR labeled KHCR. After shaping by freeze-tape casting, the porosity and stress to rupture obtained by a biaxial flexural test were collected for disk-like samples after drying and sintering at 1200 °C. Results showed that KCR ceramic materials had the highest biaxial bending strength (70 ± 1.1 MPa) and those from KORS had the highest porosity value (80 ± 1%). SEM observation revealed a difference in microstructure and texture for the manufactured porous ceramic materials. In the KCR ceramic disks, the flattened pores appeared more textured, and the primary mullite crystallites formed a rigid skeleton within the amorphous phase. KORS ceramic materials showed a small quantity of secondary mullite needles which were randomly dispersed in a vitreous phase. The relatively important vitreous phase in the porous materials of HCR led to the bulk formation of small mullite particles. The biaxial flexural strength values were related to the presence of the mullite, as well as to the microstructure (volume, morphology, and size distribution of pores) after sintering.

The current focus on renewable energy sources and the circular economy favors the thermal conversion of low-quality fuels, such as biomass and waste. However, the main limitation of their usability in the power sector is the risk of slagging, fouling, ash deposition, and high-temperature corrosion. These problems may be avoided or significantly mitigated by the application of aluminosilicate clay minerals as fuel additives. In this paper, the three most commonly occurring aluminosilicates are reviewed: kaolin, halloysite, and bentonite. Their application has been proven to minimize combustion-related problems by bonding alkalis in high-melting compounds, thus increasing ash melting temperatures, reducing ash deposition tendencies, and decreasing the particulate matter emission. Due to excellent sorption properties, aluminosilicates are also expected to fix heavy metals in ash and therefore decrease their emissions into the atmosphere. The application of aluminosilicates as fuel additives may be a key factor that increases the attractiveness of biomass and other low-quality fuels for the power sector.

Halloysite nanotubes (HNTs) are clay minerals with a tubular structure that can be used for many different applications in place of carbon nanotubes. Indeed, HNTs display low/non-toxicity, are biocompatible, and can be easily prepared. Moreover, the aluminum and silica groups present on HNTs’ inner and outer surfaces facilitate the interaction with various functional agents, such as alkalis, organosilanes, polymers, surfactants, and nanomaterials. This allows the deposition of different materials, for instance, metal and non-metal oxides, on different substrate types. This review article first briefly presents HNTs’ general structure and the various applications described in the last 20 years (e.g., drug delivery, medical implants, and energy storage). Then, it discusses in detail HNT applications for water purification (inorganic and organic pollutants). It focuses particularly on HNT-TiO2 composites that are considered very promising photocatalysts due to their high specific surface area and adsorption capacity, large pore volume, good stability, and mechanical features.

Clay minerals are historically among the most used materials with a wide variety of applications. In pharmaceutical and biomedical fields, their healing properties have always been known and used in pelotherapy and therefore attractive for their potential. In recent decades, the research has therefore focused on the systematic investigation of these properties. This review aims to describe the most relevant and recent uses of clays in the pharmaceutical and biomedical field, especially for drug delivery and tissue engineering purposes. Clay minerals, which are biocompatible and non-toxic materials, can act as carriers for active ingredients while controlling their release and increasing their bioavailability. Moreover, the combination of clays and polymers is useful as it can improve the mechanical and thermal properties of polymers, as well as induce cell adhesion and proliferation. Different types of clays, both of natural (such as montmorillonite and halloysite) and synthetic origin (layered double hydroxides and zeolites), were considered in order to compare them and to assess their advantages and different uses.

The extensive use of synthetic materials in modern society presents a great challenge to environmental and water quality. As such, numerous studies were dedicated to the removal of emerging contaminants from water using novel materials as sorbents or catalysts. With large reserves and low material costs, Earth material has also attracted great attention for contaminant removal. Halloysite is a 1:1 layered clay mineral with moderate cation exchange capacity that can be used for the removal of cationic contaminants. On the other hand, as it may bear positive charges on the aluminum hydroxyl sheets, it could be used to remove anionic contaminants. In this study, the removal of a cationic dye, methylene blue (MB), and an anionic dye, alizarin red S (ARS), from the water was evaluated from single and mixed solutions. The results suggested that from single solutions, MB removal was via cation exchange while ARS removal could have originated from anion exchange. From mixed solutions, their removal was mutually increased, which may be due to a synergistic effect in the presence of a type of charged dyes serving as counterions to enhance the sorption of dyes of opposite charges. This finding suggests that halloysite may serve as a sorbent for the removal of organic contaminants of different charges at the same time, which is a new perspective that needs further evaluation and expansion.

The healing process of chronic wounds continues to be a current clinical challenge, worsened by the risk of microbial infections and bacterial resistance to the most frequent antibiotics. In this work, non-antibiotic nanohybrids based on chlorhexidine dihydrochloride and clay minerals have been developed in order to design advanced therapeutic systems aimed to enhance wound healing in chronic lesions. To prepare the nanohybrids, two methodologies have been compared: the intercalation solution procedure and the spray-drying technique, the latter as a one-step process able to reduce preparation times. Nanohybrids were then fully studied by solid state characterization techniques. Computational calculations were also performed to assess the interactions between the drug and the clays at the molecular level. In vitro human fibroblast biocompatibility and antimicrobial activity against Staphylococcus aureus and Pseudomonas aeruginosa were assessed to check biocompatibility and potential microbicidal effects of the obtained nanomaterials. The results demonstrated the effective organic/inorganic character of the nanohybrids with homogeneous drug distribution into the clayey structures, which had been confirmed by classical mechanics calculations. Good biocompatibility and microbicidal effects were also observed, especially for the spray-dried nanohybrids. It was suggested that it could be due to a greater contact area with target cells and bacterial suspensions.

Potato thermoplastic starch (TPS) containing 1 wt.% of pure halloysite (HNT), glycerol-modified halloysite (G-HNT) or polyester plasticizer-modified halloysite (PP-HNT) was prepared by melt-extrusion. Halloysites were characterized by FTIR, SEM, TGA, and DSC. Interactions between TPS and halloysites were studied by FTIR, SEM, and DMTA. The Vicat softening temperature, tensile, and flexural properties were also determined. FTIR proved the interactions between halloysite and the organic compound as well as between starch, plasticizers and halloysites. Pure HNT had the best thermal stability, but PP-HNT showed better thermal stability than G-HNT. The addition of HNT and G-HNT improved the TPS’s thermal stability, as evidenced by significantly higher T5%. Modified TPS showed higher a Vicat softening point, suggesting better hot water resistance. Halloysite improved TPS stiffness due to higher storage modulus. However, TPS/PP-HNT had the lowest stiffness, and TPS/HNT the highest. Halloysite increased Tα and lowered Tβ due to its simultaneous reinforcing and plasticizing effect. TPS/HNT showed an additional β-relaxation peak, suggesting the formation of a new crystalline phase. The mechanical properties of TPS were also improved in the presence of both pure and modified halloysites.

Halloysite particles, with their unique multilayer nanostructure, are demonstrated here as highly efficient and readily available sorbent of heavy metals that can be easily scaled up and used in large-scale water remediation facilities. The various methods of raw material purification were applied, and their effects were verified using techniques such as BET isotherm (determination of specific surface area and size of pores), XRF analysis (composition), and SEM imaging (determination of morphology). A series of adsorption experiments for aqueous solutions of metal ions (i.e., lead, cadmium) were carried out to quantify the sorption capacity of halloysite particles for selected heavy metals. The ability of adequately activated halloysite to efficiently remove heavy metal ions from water solutions was confirmed. The value of the zeta potential of raw and purified halloysite particles in water was determined. This enables us to understand its importance for the sorption of positively charged ions (metal, organics) at various pH values. The adsorption process conducted in the pH range of 6.0–6.5 showed significant improvement compared to the acidic conditions (pH value 3.0–3.5) and resulted in a high sorption capacity of lead ions—above 24.3 mg/g for the sulphuric acid-treated sample. The atomic scale ab initio calculations revealed a significant difference in adsorption energy between the external siloxane surface and cross-sectional interlayer surface, resulting in pronounced adsorption anisotropy. A low energy barrier was calculated for the interlayer migration of heavy metals into the halloysite interior, facilitating access to the active sites in these regions, thus significantly increasing the sorption capacity and kinetics. DFT (density functional theory) calculations supporting this study allowed for predicting the sorption potential of pure halloysite structure towards heavy metals. To confront it with experimental results, it was crucial to determine proper purification conditions to obtain such a developed structure from the mineral ore. The results show a massive increase in the BET area and confirm a high sorption potential of modified halloysite towards heavy metals.

Recently, environmentally friendly and sustainable materials are being developed, searching for biocompatible and efficient materials which could be incorporated into diverse industries and fields. Natural esters are investigated and have emerged as eco-friendly high-performance alternatives to mineral fluids. This research shows the evaluations on thermal transport and tribological properties of halloysite nanotubular structures (HNS) reinforcing natural ester lubricant at various filler fractions (0.01, 0.05, and 0.10 wt.%). Nanolubricant tribotestings were evaluated under two configurations, block-on-ring, and 4-balls, to obtain the coefficient of friction (COF) and wear scar diameter (WSD), respectively. Results indicated improvements, even at merely 0.01 wt.% HNS concentration, where COF and WSD were reduced by ~66% and 8%, respectively, when compared to pure natural ester. The maximum significant improvement was observed for the 0.05 wt.% concentration, which resulted in a reduction of 87% in COF and 37% in WSD. Thermal conductivity was analyzed under a temperature scan from room temperature up to 70 °C (343 K). Results indicate that thermal conductivity is improved as the HNS concentration and testing temperature are increased. Results revealed improvements for the nanolubricants in the range of 8–16% at 50 °C (323 K) and reached a maximum of 30% at 70 °C (343 K). Therefore, this research suggests that natural ester/HNS lubricants might be used in industrial applications as green lubricants.

Halloysite nanoclay (HNC) was examined as an adsorbent for the individual and simultaneous removal of antibiotic enrofloxacin (ENRO) and methylene blue (MB) from aqueous solutions, alongside its regeneration via cold atmospheric plasma (CAP) bubbling. Initially, batch kinetics and isotherm studies were carried out, while the effect of several parameters was evaluated. Both ENRO and MB adsorption onto HNC was better described by Langmuir model, with its maximum adsorption capacity being 34.80 and 27.66 mg/g, respectively. A Pseudo-second order model fitted the experimental data satisfactorily, suggesting chemisorption (through electrostatic interactions) as the prevailing adsorption mechanism, whereas adsorption was also controlled by film diffusion. In the binary system, the presence of MB seemed to act antagonistically to the adsorption of ENRO. The saturated adsorbent was regenerated inside a CAP microbubble reactor and its adsorption capacity was re-tested by applying new adsorption cycles. CAP bubbling was able to efficiently regenerate saturated HNC with low energy requirements (16.67 Wh/g-adsorbent) in contrast to Fenton oxidation. Most importantly, the enhanced adsorption capacity of the CAP-regenerated HNC (compared to raw HNC), when applied in new adsorption cycles, indicated its activation during the regeneration process. The present study provides a green, sustainable and highly effective alternative for water remediation where pharmaceutical and dyes co-exist.

Fluid catalytic cracking (FCC) is a production process that converts petroleum into petroleum products in the presence of catalysts. The performance of an FCC catalyst plays a decisive role in petroleum refining. An FCC catalyst mainly comprises a molecular sieve (catalytic cracking active center), a carrier, and a binder. The carrier can enable the precracking of the heavy oil in its large pore, which can improve the overall activity of the catalyst and the conversion rate of heavy oil. The surface area and pore structure of carrier materials with different microscopic morphologies differ, which significantly affects the precracking of heavy oil molecules. Therefore, here, FCC catalysts were prepared using flake kaolinite, tubular halloysite, natural flake-tube-combined kaolinite, and mixed kaolinite as support materials, respectively. The FCC catalysts were used in FCC-heavy oil, and the influence of the carrier material morphology on the comprehensive performance of the catalysts was studied. The strength and cracking performance of the catalyst prepared using flake Maoming (M) were poor, whereas the catalyst prepared using tubular halloysite exhibited a good strength, high activity, and a good cracking ability for heavy oil. The catalyst prepared using natural flake-tube combined with Suzhou (S) exhibited a good strength and cracking performance, and it has been widely used in the industrial production of FCC catalysts. When 40% tube-like halloysite was mixed into M, the attrition of the prepared catalyst decreased by 0.5 units, the microreactivity increased by 1.4 units, the gasoline + liquefied petroleum gas (LPG) yield increased by 3.09 percentage points, and the gasoline research octane number (RON) increased by 0.6 units. The comprehensive performance of the catalyst can reach or exceed that of the natural-lamp-tube-based kaolin carrier. The results can not only provide guidance for the stable quality control of kaolin, but they can also significantly alleviate the resource restrictions for FCC catalyst production enterprises.

The concept of this study is the replacement of previous fossil-based techniques for food packaging and food shelf-life extension, with novel more green processes and materials following the spirit of circular economy and the global trend for environmentally positive fingerprints. A novel adsorption process to produce thymol-halloysite nanohybrids is presented in this work. The high dispersion of this thymol-halloysite nanostructure in chitosan biopolymer is one of the goals of this study. The incorporation of this biodegradable matrix with poly-vinyl-alcohol produced a very promising food-packaging film. Mechanical, water-oxygen barrier, antimicrobial, and antioxidant properties were measured. Transparency levels were also tested using a UV-vis instrument. Moreover, the developed films were tested in-vivo for the preservation and the extension of the shelf-life of kiwi fruits. In all cases, results indicated that the increased fraction of thymol from thyme oil significantly enhances the antimicrobial and antioxidant activity of the prepared chitosan-poly-vinyl- alcohol gel. The use of the halloysite increases the mechanical and water-oxygen barrier properties and leads to a control release process of thymol which extends the preservation and the shelf-life of kiwi fruits. Finally, the results indicated that the halloysite improves the properties of the chitosan/poly-vinyl-alcohol films, and the thymol makes them further advantageous.

A new drug delivery system consisting of clindamycin phosphate entrapped in acid-etched halloysite nanotubes was successfully prepared and characterized. It was then used as an antibacterial component of the multicomponent hydrogel designed as a material for bone regeneration. First, halloysite (HNT) was etched and clindamycin phosphate (CP) was entrapped in both raw and modified nanotubes, resulting in HNT-CP and EHNT-CP systems. They were characterized using SEM, TEM, TGA and FTIR; the entrapment efficiency and release of CP from both systems were also studied. EHNT-CP was then used as an antibacterial component of the two hydrogels composed of alginate, collagen and β-TCP. The hydrogels were prepared using different crosslinking procedures but had the same composition. The morphology, porosity, degradation rate, CP release profile, cytocompatibility, antibacterial activity and ability to induce biomineralization were studied for both materials. The hydrogel obtained by a chemical crosslinking with EDC followed by the physical crosslinking with calcium ions had better properties and was shown to have potential as a bone repair material.

The global spread of antibiotic-resistant strains, and the need to protect the microflora from non-specific antibiotics require more effective and selective alternatives. In this work, we demonstrate for the first time a superior antibacterial photothermal effect of plasmonic gold nanorods (AuNRs) via their incorporation onto natural clay halloysite nanotubes (HNTs), which were functionalized with anti-E. coli antibodies (Ab-HNTs). AuNRs were incorporated onto the Ab-HNTs through a facile freeze–thaw cycle, and antibody integrity following the incorporation was confirmed via infrared spectroscopy and fluorescence immunolabeling. The incorporation efficiency was studied using UV-Vis absorption and transmission electron microscopy (TEM). Mixtures of E. coli and AuNR-Ab-HNTs hybrids or free AuNRs were irradiated with an 808 nm laser at 3–4 W cm−2, and the resulting photothermal antibacterial activity was measured via plate count. The irradiated AuNR-Ab-HNTs hybrids exerted an 8-fold higher antibacterial effect compared to free AuNR under 3.5 W cm−2; whereas the latter induced a 6 °C-higher temperature elevation. No significant antibacterial activity was observed for the AuNR-Ab-HNTs hybrid against non-target bacteria species (Serratia marcescens and Staphylococcus epidermidis). These findings are ascribed to the localization of the photothermal ablation due to the binding of the antibody-functionalized clay to its target bacteria, as supported through TEM imaging. In the future, the HNTs-based selective carriers presented herein could be tailored with other antibacterial nanoparticles or against another microorganism via the facile adjustment of the immobilized antibody.

Methyl Violet (MV) was removed from aqueous solutions by adsorption onto halloysite nanoclay (HNC) employing equilibrium, kinetics, thermodynamic data, molecular modellingR (MD), and Monte Carlo (MC) simulations. The chosen experimental variables were pH, temperature, starting MV concentration, contact time, and adsorbent dosage. The adsorption rate was determined to increase with increasing contact time, initial dye concentration, pH, and temperature. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich (D-R) isotherms were utilized to determine the adsorption capacity of HNC. The Langmuir equation matched equilibrium data better than the other models, whereas the pseudo-second-order model better described kinetic data, and thermodynamic analyses revealed that the adsorption process was spontaneous, endothermic, and physisorption-based. This study focused on two distinct molecular mechanics-based theoretical approaches (MC and MD). These techniques enabled a molecular comprehension of the interaction between the MV molecule and the halloysite surface. Theoretical results were consistent with experimental findings. The outcomes revealed that HNC is an excellent dye adsorbent for industrial effluents.

A novel voltammetric method for the sensitive and selective determination of cadmium and lead ions using screen-printed carbon electrodes (SPCEs) modified with carbon-deposited natural halloysite (C_Hal) and multi-walled carbon nanotubes (MWCNTs) was developed. The electrochemical properties of the proposed sensor were investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV), while the morphology and structure were established by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). A two-factorial central composite design (CCD) was employed to select the composition of the nanocomposite modifying the electrode surface. The optimal measuring parameters of differential pulse anodic stripping voltammetry (DPASV) used for quantitative analysis were established with the Nelder–Mead simplex method. In the analytical investigation of Cd(II) and Pb(II) ions by DPASV, the MWCNTs/C_Hal/Nafion/SPCE exhibited a linear response in the concentration range of 0.1–10.0 µmol L−1 (for both ions) with a detection limit of 0.0051 and 0.0106 µmol L−1 for Pb(II) and Cd(II), respectively. The proposed sensor was successfully applied for the determination of metal ions in different natural water and honey samples with recovery values of 96.4–101.6%.

Hollow carbon nanocapsules have been attracting growing interest due to their fascinating characteristics and extensive potential applications. In this work, a novel natural halloysite-templated synthesis approach for highly graphitic boron-doped hollow carbon nanocapsule webs (B-HCNCWs) using glucose as the carbon source and boric acid as the heteroatom dopant was first reported. The formation process and physicochemical properties of B-HCNCWs were revealed by SEM, TEM, XRD, Raman, Brunauer–Emmett–Teller (BET), and XPS characterization techniques. The outcomes showed that the as-obtained B-HCNCWs with hollow nanocapsule network architecture had a specific surface area of 263 m2 g−1, a pore volume of 0.8 cm3 g−1, a high degree of graphitization (81.4%), graphite-like interplanar spacing (0.3370 nm), and B-containing functional groups (0.77 at%). The density function theory (DFT) calculation demonstrated that the adsorption energies of Li on B-HCNCWs were much higher than that of HCNCWs, which proved that B-doping in a carbon matrix could increase the lithium intercalation capacity.

Inactivation of bacteria under the influence of visible light in presence of nanostructured materials is an alternative approach to overcome the serious problem of the growing resistance of pathogenic bacteria to antibiotics. Cadmium sulfide quantum dots are superefficient photocatalytic material suitable for visible light transformation. In this work, CdS nanoparticles with size of less than 10 nm (QDs) were synthesized on the surface of natural and synthetic mesoporous aluminosilicates and silicates (halloysite nanotubes, MCM-41, MCM-41/Halloysite, SBA-15). Materials containing 5–7 wt.% of CdS were characterized and tested as agents for photocatalytic bacteria degradation of Gram-positive S. aureus and Gram-negative E. coli with multiple antibiotic resistance. Eukaryotic cell viability tests were also conducted on the model cancer cells A 459. We found that the carrier affects prokaryotic and eukaryotic toxicity of CdS quantum dots. CdS/MCM-41/HNTs were assumed to be less toxic to eukaryotic cells and possess the most prominent photocatalytic antibacterial efficiency. Under visible light irradiation, it induced 100% bacterial growth inhibition at the concentration of 125 μg/mL and the bacteriostatic effect at the concentration of 63 μg/mL. CdS/MCM-41/HNTs showed 100% E. coli growth inhibition in the concentration of 1000 μg/mL under visible light irradiation.

The global turn from the linear to the circular economy imposes changes in common activities such as food packaging. The use of biodegradable materials such as polyvinyl alcohol, natural raw materials such as clays, and food byproducts such as chitosan to develop novel food packaging films attracts the interest of industrial and institutional research centers. In this study, novel hybrid nanostructures were synthesized via the growth of zinc oxide nanorods on the surface of two nanoclays. The obtained nanostructures were incorporated with chitosan/polyvinyl alcohol composite either as nanoreinforcement or as an active agent to develop packaging films. The developed films were characterized via XRD, FTIR, mechanical, water-vapor diffusion, water sorption, and oxygen permeability measurements. Antimicrobial activity measurements were carried out against four different pathogen microorganisms. XRD indicated the formation of an intercalated nanocomposite structure for both types of nanoclays. Furthermore, improved tensile, water/oxygen barrier, and antimicrobial properties were recorded for all films compared to the pure chitosan/polyvinyl alcohol film. Overall, the results indicated that the use of the bio-based developed films led to an extension of food shelf life and could be used as novel active food packaging materials. Among them, the most promising film was the 6% wt. ZnO@halloysite.

In the framework of designing a novel bio-coating for the preservation of fresh fruits, this paper reports the design, preparation, and characterization of novel bio-nanocomposites based on pectin loaded with grapefruit seed oil (GO), a natural compound with antimicrobial properties, encapsulated into halloysite nanotubes (HNTs). The vacuum-based methodology was used for the encapsulation of the oil into the hollow area of the nanotubes, obtaining nano-hybrids (HNT-GO) with oil concentrations equal to 20, 30, and 50 wt%. Physical properties (thermal, mechanical, barrier, optical) were analyzed. Thermal properties were not significantly (p < 0.05) affected by the filler, while an improvement in mechanical performance (increase in elastic modulus, stress at breaking, and deformation at breaking up to 200%, 48%, and 39%, respectively, compared to pure pectin film) and barrier properties (increase in water permeability up to 480% with respect to pure pectin film) was observed. A slight increase in opacity was detected without significantly compromising the transparency of the films. The release of linoleic acid, the main component of GO, was followed for 21 days and was correlated with the amount of the hybrid filler, demonstrating the possibility of tailoring the release kinetic of active molecules. In order to evaluate the effectiveness of the prepared bio-composites as an active coating, fresh strawberries were coated and compared to uncoated fruit. Qualitative results showed that the fabricated novel bio-coating efficiently extended the preservation of fresh fruit.

A broad-spectrum antimicrobial respiration apparatus designed to fight bacteria, viruses, fungi, and other biological agents is critical in halting the current pandemic’s trajectory and containing future outbreaks. We applied a simple and effective electrodeposition method for metal (copper, silver, and zinc) coating the surface of halloysite nanotubes (HNTs). These nanoparticles are known to possess potent antiviral and antimicrobial properties. Metal-coated HNTs (mHNTs) were then added to polylactic acid (PLA) and extruded to form an mHNT/PLA 3D composite printer filament. Our composite 3D printer filament was then used to fabricate an N95-style mask with an interchangeable/replaceable filter with surfaces designed to inactivate a virus and kill bacteria on contact, thus reducing deadly infections. The filter, made of a multilayered antimicrobial/mHNT blow spun polymer and fabric, is disposable, while the mask can be sanitized and reused. We used several in vitro means of assessing critical clinical features and assessed the bacterial growth inhibition against commonly encountered bacterial strains. These tests demonstrated the capability of our antimicrobial filament to fabricate N95 masks and filters that possessed antibacterial capabilities against both Gram-negative and Gram-positive bacteria.

Due to its slow degradation rate, polycaprolactone (PCL) is frequently used in biomedical applications. This study deals with the development of antibacterial nanofibers based on PCL and halloysite nanotubes (HNTs). Thanks to a combination with HNTs, the prepared nanofibers can be used as low-cost nanocontainers for the encapsulation of a wide variety of substances, including drugs, enzymes, and DNA. In our work, HNTs were used as a nanocarrier for erythromycin (ERY) as a model antibacterial active compound with a wide range of antibacterial activity. Nanofibers based on PCL and HNT/ERY were prepared by electrospinning. The antibacterial activity was evaluated as a sterile zone of inhibition around the PCL nanofibers containing 7.0 wt.% HNT/ERY. The morphology was observed with SEM and TEM. The efficiency of HNT/ERY loading was evaluated with thermogravimetric analysis. It was found that the nanofibers exhibited outstanding antibacterial properties and inhibited both Gram- (Escherichia coli) and Gram+ (Staphylococcus aureus) bacteria. Moreover, a significant enhancement of mechanical properties was achieved. The potential uses of antibacterial, environmentally friendly, nontoxic, biodegradable PCL/HNT/ERY nanofiber materials are mainly in tissue engineering, wound healing, the prevention of bacterial infections, and other biomedical applications.

A new, innovative approach in the search for an effective and cheap carbon dioxide sorbent, in line with the circular economy and sustainable development principles, directs the attention of researchers to various types of waste ashes generated as a result of biomass combustion. In addition to the use of environmentally safe materials that have been experimentally identified, and that, in some way, have adjustable sorption capacity, it is also possible to rationally develop a widely applicable, simple, and inexpensive technology based on large amounts of this type of post-industrial waste, which is also an equally important issue for the natural environment (reducing the need for ash storage and accumulation). Even the lower sorption capacity can be successfully compensated for by their common availability and very low cost. Thus, the CO2 adsorption capability of the ashes from the combustion of straw biomass was experimentally investigated with the use of a high-pressure adsorption stand. The presented original technological concept has been positively verified on a laboratory scale, thus a functionalization-based approach to the combustion of substrate mixtures with nano-structural additives (raw, dried, calcined halloysite, kaolinite), introduced to improve the performance of straw biomass combustion and bottom ash formation in power boilers, clearly increased the CO2 adsorption capacity of the modified ashes. This allows for an advantageous synergy effect in the extra side-production of useful adsorbents in the closed-loop “cascade” scheme of the CE process. The addition of 4 wt.% kaolinite to straw biomass caused an over 2.5-fold increase in the CO2 adsorption capacity in relation to ash from the combustion of pure straw biomass (with a CO2 adsorption capacity of 0.132 mmol/g). In the case of addition of 4 wt.% nano-structured species to the straw combustion process, the best effects (ash adsorption capacity) were obtained in the following order: kaolinite (0.321 mmol/g), raw halloysite (0.310 mmol/g), calcined halloysite (0.298 mmol/g), and dried halloysite (0.288 mmol/g). Increasing the dose (in relation to all four tested substances) of the straw biomass additive from 2 to 4 wt.%, not only increase the adsorption capacity of the obtained ash, thus enriched with nano-structural additives, but also a showed a significant reduction in the differences between the maximum adsorption capacity of each ash is observed. The experimental results were analyzed using five models of adsorption isotherms: Freundlich, Langmuir, Jovanović, Temkin, and Hill. Moreover, selected samples of each ash were subjected to porosimetry tests and identification of the surface morphology (SEM). The obtained results can be used in the design of PSA processes or as permanent CO2 adsorbents, based on the environmentally beneficial option of using ashes from biomass combustion with appropriately selected additives.

There is a potential for using sulfur waste in agriculture. The main objective of this study was to design a granular fertilizer based on waste elemental sulfur. Humic acids and halloysite were used to improve the properties and their influence on soil properties. This is the first report on the use of proposed materials for fertilizer production. The following granular fertilizers were prepared (the percentage share of component weight is given in brackets): fertilizer A (waste sulfur (95%) + halloysite (5%)), fertilizer B (waste sulfur (81%) + halloysite (5%) + humic acids (14%)), fertilizer C (waste sulfur (50%) + halloysite (50%)) and fertilizer D (waste sulfur (46%) + halloysite (46%) + humic acids (8%)). Basic properties of the obtained granulates were determined. Furthermore, the effect of the addition of the prepared fertilizers on soil pH, electrolytic conductivity, and sulfate content was examined in a 90-day incubation experiment. Enrichment with humic acids and the higher amount of halloysite increased the fertilizer properties (especially the share of larger granules and bulk density). In addition, it stabilized soil pH and increased the sulfur content (extracted with 0.01 mol·L−1 CaCl2 and Mehlich 3) in the soil.

Halloysite nanotube (HNT) which is cheap, natural, and easily accessible 1D clay, can be used in many applications, particularly heat transfer enhancement. The aim of this research is to study experimentally the pool boiling heat transfer (PBHT) performance of novel halloysite nanofluids at atmospheric pressure condition from typical horizontal heater. The nanofluids are prepared from halloysite nanotubes (HNTs) nanomaterials-based deionized water (DI water) with the presence of sodium hydroxide (NaOH) solution to control pH = 12 to obtain stable nanofluid. The nanofluids were prepared with dilute volume concentrations of 0.01–0.5 vol%. The performance of PBHT is studied via pool boiling curve and pool boiling heat transfer coefficient (PBHTC) from the typical heater which is the copper horizontal tube with a thickness of 1 mm and a diameter of 22 mm. The temperatures of the heated tube surface are measured to obtain the PBHTC. The results show an improvement of PBHTC for halloysite nanofluids compared to the base fluid. At 0.05 vol% concentration, HNT nanofluid has the best enhancement of 5.8% at moderate heat flux (HF). This indicates that HNT is a potential material in heat transfer applications.

In recent years, nanomaterials have attracted significant research interest for applications in biomedicine. Many kinds of engineered nanomaterials, such as lipid nanoparticles, polymeric nanoparticles, porous nanomaterials, silica, and clay nanoparticles, have been investigated for use in drug delivery systems, regenerative medicine, and scaffolds for tissue engineering. Some of the most attractive nanoparticles for biomedical applications are nanoclays. According to their mineralogical composition, approximately 30 different nanoclays exist, and the more commonly used clays are bentonite, halloysite, kaolinite, laponite, and montmorillonite. For millennia, clay minerals have been extensively investigated for use in antidiarrhea solutions, anti-inflammatory agents, blood purification, reducing infections, and healing of stomach ulcers. This widespread use is due to their high porosity, surface properties, large surface area, excellent biocompatibility, the potential for sustained drug release, thermal and chemical stability. We begin this review by discussing the major nanoclay types and their application in biomedicine, focusing on current research areas for halloysite in biomedicine. Finally, recent trends and future directions in HNT research for biomedical application are explored.

Tubular halloysite (HNT) is a naturally occurring aluminosilicate clay with a unique combination of natural availability, good biocompatibility, high mechanical strength, and functionality. This study explored the effects of magnetically responsive halloysite (MHNT) on the structure, morphology, chemical composition, and magnetic and mechanical properties of electrospun nanofibers based on polycaprolactone (PCL) and gelatine (Gel) blends. MHNT was prepared via a simple modification of HNT with a perchloric-acid-stabilized magnetic fluid–methanol mixture. PCL/Gel nanofibers containing 6, 9, and 12 wt.% HNT and MHNT were prepared via an electrospinning process, respecting the essential rules for medical applications. The structure and properties of the prepared nanofibers were studied using infrared spectroscopy (ATR-FTIR) and electron microscopy (SEM, STEM) along with energy-dispersive X-ray spectroscopy (EDX), magnetometry, and mechanical analysis. It was found that the incorporation of the studied concentrations of MHNT into PCL/Gel nanofibers led to soft magnetic biocompatible materials with a saturation magnetization of 0.67 emu/g and coercivity of 15 Oe for nanofibers with 12 wt.% MHNT. Moreover, by applying both HNT and MHNT, an improvement of the nanofibers structure was observed, together with strong reinforcing effects. The greatest improvement was observed for nanofibers containing 9 wt.% MHNT when increases in tensile strength reached more than two-fold and the elongation at break reached a five-fold improvement.

Rapidly growing 3D printing of hydrogels requires network materials which combine enhanced mechanical properties and printability. One of the most promising approaches to strengthen the hydrogels consists of the incorporation of inorganic fillers. In this paper, the rheological properties important for 3D printability were studied for nanocomposite hydrogels based on a rigid network of percolating halloysite nanotubes embedded in a soft alginate network cross-linked by calcium ions. Particular attention was paid to the effect of polymer cross-linking on these properties. It was revealed that the system possessed a pronounced shear-thinning behavior accompanied by a viscosity drop of 4–5 orders of magnitude. The polymer cross-links enhanced the shear-thinning properties and accelerated the viscosity recovery at rest so that the system could regain 96% of viscosity in only 18 s. Increasing the cross-linking of the soft network also enhanced the storage modulus of the nanocomposite system by up to 2 kPa. Through SAXS data, it was shown that at cross-linking, the junction zones consisting of fragments of two laterally aligned polymer chains were formed, which should have provided additional strength to the hydrogel. At the same time, the cross-linking of the soft network only slightly affected the yield stress, which seemed to be mainly determined by the rigid percolation network of nanotubes and reached 327 Pa. These properties make the alginate/halloysite hydrogels very promising for 3D printing, in particular, for biomedical purposes taking into account the natural origin, low toxicity, and good biocompatibility of both components.

In this study, an ionic liquid (IL), 1-butyl-3-methylimidazolium acetate, was used to prepare ionogels with microcrystalline cellulose (MCC) and halloysite (Hal). SEM, XRD, TG, DSC, FTIR spectroscopy, conductometry and mechanical tests were used to study the morphology, structure, thermal behaviour and electrophysical and mechanical characteristics of synthesised ionogels. XRD analysis showed a slight decrease in the interlayer space of halloysite in ionogels containing MCC, which may have been associated with the removal of residual water molecules resulting from hydrophilic IL anions and polymer macromolecules. A change in conductivity and glass-transition temperature of the ionic liquid was revealed due to intercalation into halloysite (a confinement effect) and modification with cellulose. For triple IL/Hal/MCC ionogels, the characteristic thermal degradation temperatures were higher than the corresponding values for IL/Hal composites. This indicates that the synthesised IL/Hal/MCC ionogels are characterised by a greater thermal stability than those of IL/Hal systems.

To address the problem of ever-increasing oily wastewater management, due to its directional liquid transport property, membranes with asymmetric wettability can be effectively used for emulsion separation. This study reports the synthesis of electrospun polymer–clay nanocomposite nanofibers, using co-polyamide polymer (COPA) and halloysite nanotubes (HA) as filler. The influence of clay content on the morphological, thermal and dielectric properties of the polymer composite nanofiber was investigated comprehensively to address the material characteristics of the developed system. The surface structure analysis and contact angle measurements of the electrospun composite nanofibers confirms the change in surface roughness and wettability when the fillers are added to the polymer. The porosity of the composite electrospun nanofiber membrane was found to be 85% with an oil adsorption capacity of 97% and water permeability of 6265 L/m2 h. Furthermore, the asymmetric wettability-driven oil/water emulsion separation abilities of the as-synthesized membranes shows that the separation efficiency of the composite fiber membrane is 10% improved compared to that of the neat fiber membrane, with improved separation time.

Due to the fact that the application of AW and EP additives in low-temperature greases may lead to worse high-temperature and anti-corrosion characteristics as well as additional burden on the environment due to the content of aggressive components, in this paper, the possibility of replacing these additives with NFA, which do not have these disadvantages, was investigated. The analysis of nanosized particles being used as functional additives in greases was carried out. The morphology of the following nanoparticles was studied: montmorillonite K 10, silica, calcium car-bonate and borate, halloysite, and molybdenum disulfide incorporated in halloysite tubes. The effect of nanostructured components on the physicochemical characteristics and anti-wear and anti-scuffing properties of complex lithium, polyurea, and polymer greases were studied. Maximal improvement of anti-wear and anti-scuffing characteristics of cLi-greases was reached when using silica and calcium borate. Maximal improvement of anti-scuffing properties of PU-lubricant was reached when using calcium carbonate and the two-component NFA based on halloysite, for anti-wear properties when adding silicon dioxide and halloysite. When the concentrations of silicon dioxide and calcium carbonate was increased from 1 to 3 wt.%, there was a decrease in yield stress of the structural frame of the PU-lubricant and its colloidal stability was worse. The increase of the concentration of calcium carbonate and borate nanoparticles in the studied range led to a significant improvement of the anti-wear and anti-scuffing characteristics of the PU grease, respectively. The greases properties’ dependence from the nanostructured functional additives’ introduction method and their concentration were investigated. Nanoparticles were added into the test lubricants before and after the thermo-mechanical dispersion stage. The addition of silicon dioxide and calcium carbonate NFA after the heat treatment stage led to worsening of the characteristics of the plastic material, and the increase of their concentration from 1 to 3 wt.% formed a harder structure of Li-grease. On the contrary, the addition of calcium borate NFA is recommended after the thermomechanical dispersion. The choice of nanoparticles and the method of their addition to the lubricants of various types was carried out according to the results of the previous stage of the research. Along with the analysis of the physicochemical characteristics and anti-wear and anti-scuffing properties of the lubricants, the structure of the dispersion phase of nanomodified lubricants were studied.

Halloysite is a promising building block in nanoarchitectonics of functional materials, especially in the development of novel biomaterials and smart coatings. Understanding the behavior of materials produced using halloysite nanotubes within living organisms is essential for their safe applications. In this study, quantum dots of different compositions were synthesized on the surface of modified clay nanotubes, and the biodistribution of this hybrid material was monitored within Caenorhabditis elegans nematodes. The influence of the modification agent as well as the particles’ composition on physicochemical properties of hybrid nanomaterials was investigated. Several microscopy techniques, such as fluorescence and dark-field microscopy, were compared in monitoring the distribution of nanomaterials in nematodes’ organisms. The effects of QDs-halloysite composites on the nematodes’ life cycle were investigated in vivo. Our fluorescent hybrid probes induced no acute toxic effects in model organisms. The stable fluorescence and low toxicity towards the organisms suggest that the proposed synthesis procedure yields safe nanoarchitectonic materials that will be helpful in monitoring the behavior of nanomaterials inside living cells and organisms.

The increased demands of our rapidly developing way of life lead to the broadening of the ceramic market among other effects. Due to the advanced ceramic properties of halloysite and its abundance, combined with its good synergistic effect with other materials, it has been investigated for multifarious possible applications to produce traditional and advanced ceramics as well as ceramic composites. In this review, a substantial number of studies by several investigators into halloysite-based ceramics were are summarized. The possibilities and limitations of different halloysite-based ceramic materials for future applications are also discussed in this manuscript and new fields of research are proposed. The summarization of published results indicates a constant scientific interest in halloysite-based traditional ceramics and new potential uses in the future. Additionally, investigations on different novel ceramic composites with low cost halloysite nanotubes (HNTS) have rapidly increased, covering different scientific and technological areas. On the other hand, research into advanced ceramics (SiAlONS) has been pursued due to its highly cost effective technology treatments on a large scale.

Topical administration of drugs is required for the treatment of parasitic diseases and insect infestations; therefore, fabrication of nanoscale drug carriers for effective insecticide topical delivery is needed. Here we report the enhanced immobilization of halloysite tubule nanoclay onto semiaquatic capybaras which have hydrophobic hair surfaces as compared to their close relatives, land-dwelling guinea pigs, and other agricultural livestock. The hair surface of mammals varies in hydrophobicity having a cortex surrounded by cuticles. Spontaneous 1–2 µm thick halloysite hair coverages on the semi-aquatic rodent capybara, non-aquatic rodent guinea pig, and farm goats were compared. The best coating was found for capybara due to the elevated 5 wt% wax content. As a result, we suggest hair pretreatment with diluted wax for enhanced nanoclay adsorption. The formation of a stable goat hair coverage with a 2–3 µm halloysite layer loaded with permethrin insecticide allowed for long-lasting anti-parasitic protection, enduring multiple rain wettings and washings. We expect that our technology will find applications in animal parasitosis protection and may be extended to prolonged human anti-lice treatment.

A novel chitosan/grafted halloysitenanotubes@Znγmagnetite quaternary nanocomposite (Ch/g-HNTs@ZnγM) was fabricated using the chemical co-precipitation method to remove the ions of Cr (III), Fe (III), and Mn (II) from wastewater. The characteristics of the synthesized Ch/g-HNTs@ZnγM quaternary nanocomposite were investigated using FTIR, SEM, XRD, GPC, TGA, TEM, and surface zeta potential. The characterization analysis proved that the mentioned nanocomposite structure contains multiple functional groups with variable efficiencies. Additionally, they proved the existence of magnetic iron in the nanocomposite internal structure with the clarity of presentation of gaps and holes of high electron density on its surface. The results showed that the pH and time to reach an equilibrium system for all the studied metal ions were obtained at 9.0 and 60 min, respectively. The synthesized Ch/g-HNTs@ZnγM nanocomposite exhibited maximum adsorption removal of 95.2%, 99.06%, and 87.1% for Cr (III), Fe (III), and Mn (II) ions, respectively. The pseudo-second-order kinetic model and, for isotherm, the Langmuir model were best fitted with the experimental data. The thermodynamic parameters indicated the exothermic and spontaneous nature of the adsorption reaction as proven by the ΔH° and ΔG° values. Additionally, chemical adsorption by the coordination bond is supposed as the main mechanism of adsorption of the mentioned metal ions on the nanocomposite. Finally, Ch/g-HNTs@ZnγM displays prospected advantages, such as a low-expense adsorbent, high efficiency and availability, and an eco-friendly source, that will reduce the environmental load via an environmentally friendly method.

In this work, raw halloysite mineral from Dunino (Poland) has been characterized and tested as an efficient and low-cost adsorbent for dye removal from water. The morphology and structure of this clay were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and the chemical composition was evaluated by means of X-ray fluorescence spectroscopy (XRF), energy dispersive X-ray spectroscopy (EDX), and electron energy loss spectroscopy (EELS). The results showed that it is made up of both platy and tubular structures, mainly composed of Si, Al, and O. Iron oxide particles covering the platy structures were also observed. The surface charge of halloysite was measured by z-potential measurements and by the evaluation of the point of zero charge. The clay was tested as an adsorbent for the removal of positively and negatively charged dye molecules, i.e., methylene blue (MB) and methyl orange (MO), both separately and in a mixed-dye solution. Halloysite showed the ability to efficiently and selectively remove MB molecules by adsorption, both in a single-dye solution and in a mixed one. The adsorption of positive dyes on the clay surface mainly occurred through ion exchange at negatively charged sites on its surface. The possibility of regenerating the clay for further dye removal processes is also shown.

The aim of the study was to determine the effect of supplementing broiler chickens’ diets with halloysite on daily body weight gain (BWG), feed conversion ratio (FCR), daily water consumption (DWC), and some broiler house hygiene parameters. The trial was conducted on 18,000 broiler chickens divided into two groups throughout the 42-day (D) rearing period. The birds were fed complete diets without (group C) or with halloysite addition (1%, group E) from D8 of rearing. No difference in the mortality rate was observed between groups C and E. Birds from group E had a tendency (0.05 < p < 0.10) towards a higher body weight at D32 and D42, a higher BWG, and a lower FCR compared to group C during the entire rearing period. Average DWC differed only in the finisher period, with a tendency towards lower overall DWC in group E. The concentration of ammonia in the air from D21 to D35 was increased more than 5-fold in group C but only 1.5-fold in group E. In conclusion, the use of halloysite as a feed additive in the diet of broiler chickens resulted in a reduction in feed consumption per unit of BWG and higher utilisation of crude protein, which led to improved environmental conditions.

Low-cost urea formaldehyde resin (UF)/reactive halloysite nanotubes (HNTs) nanocomposite adhesive was prepared successfully via in situ polymerization. The HNTs were modified to improve its compatibility with polymer. The XRD and FTIR results showed that physical and chemical interaction between the HNTs and polymer resin influenced the structure of UF owing to the functional groups on the HNTs. It is found from SEM images that the modified HNTs could be dispersed uniformly in the resin and the nanocomposite particles were spherical. The performance experiment confirmed that thermal stability of nanocomposite increased largely, formaldehyde emission of UF wood adhesive reduced 62%, and water resistance of UF wood adhesive improved by 84%. Meanwhile, the content of HNTs on the nanocomposites could be up to 60 wt %. The mechanism of the nanocomposites based on the reactive HNTs was proposed. The approach of the preparation could supply an idea to prepare other polymer/clay nanocomposites.