Study of the Diffusion Behavior of Seawater Absorption in Multi-Walled Carbon Nanotubes/Halloysite Nanotubes Hybrid Nanofillers Modified Epoxy-Based Glass/Carbon Fiber Composites

In the maritime industry, cost-effective and lightweight Fiber Reinforced Polymer (FRP) composites offer excellent mechanical properties, design flexibility, and corrosion resistance. However, their reliability in harsh seawater conditions is a concern. Researchers address this by exploring three approaches: coating fiber surfaces, hybridizing fibers and matrices with or without nanofillers, and interply rearrangement. This study focuses on evaluating the synergistic effects of interply rearrangement of glass/carbon fibers and hybrid nanofillers, specifically Multi-walled carbon nanotubes (MWCNT) and Halloysite nanotubes (HNT). The aim is to enhance impact properties by minimizing moisture absorption. Hybrid nanocomposites with equal-weight proportions of two nanofillers: 0 wt.%, 1 wt.%, and 2 wt.% were exposed to seawater for 90 days. Experimental data was subjected to modelling through the application of Predictive Fick’s Law. The study found that the hybrid composite containing 2 wt.% hybrid nanofillers exhibited a 22.10% increase in impact performance compared to non-modified counterparts. After 90 days of seawater aging, the material exhibited enhanced resistance to moisture absorption (15.74%) and minimal reduction in impact strength (8.52%) compared to its dry strength, with lower diffusion coefficients.

In-situ incorporation of halloysite nanotubes with 2D zeolitic imidazolate framework-L based membrane for dye/salt separation

Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial ability,but the dense accumulation on the membrane surface and the low permeate flux greatly hinder their application.Herein,we synthesized m HNTs(modified halloysite nanotubes)/ZIF-L nanocomposites on modified m HNTs by in situ growth method.Interestingly,due to the different size of m HNTs and ZIF-L,m HNTs were packed in ZIF-L nanosheets.The hollow m HNTs provided additional transport channels for water molecules,and the accumulation of the ZIF-L nanosheets was decreased after assembling m HNTs/ZIF-L nanocomposites into membrane by filtration.The prepared m HNTs/ZIF-L membrane presented high permeate flux(59.6 L·m^(-2)·h^(-1)),which is 2-4 times of the ZIF-L membranes(14.8 L·m^(-2)·h^(-1)).Moreover,m HNTs/ZIF-L membranes are intrinsically antimicrobial,which exhibit extremely high bacterial resistance.We provide a controllable strategy to improve 2D ZIF-L assembles,and develops novel membranes using 2D package structure as building units.

Two-Dimensional Co_(2)(OH)1,4-Benzenedicarboxylate-Halloysite Nanotube Nanocomposite-Epoxy Coating with High Corrosion Resistance

Introducing inorganic nanomaterials into a polymer matrix greatly improves the anticorrosion performance of epoxy coatings(EP);however,poor compatibility between the materials can limit the improvement in properties.In this work,based on the high interface compatibility of two-dimensional(2D)Co_(2)(OH)_(2)BDC(BDC=1,4-benzenedicarboxylate)in the epoxy coating that we reported in previous work,we fabricated a 2D Co_(2)(OH)_(2)BDC-halloysite nanotube(HNT)nanocomposite have a structure consisting of alternating of nanosheets and nanotube by in situ synthesis.The nanocomposite was characterized by Fourier transform infrared spectroscopy,X-ray diffraction,and scanning electron microscopy.The mechanical and anticorrosion performance of the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was evaluated by mechanical tests and electrochemical impedance spectroscopy spectra.Compared with a conventional unreinforced epoxy coating,the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating had higher mechanical strength and toughness,and the low-frequency impedance modulus of 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was increased by three orders of magnitude,demonstrating the high corrosion resistance of our reinforced coating.

Evaluation of self-healing properties of inhibitor loaded nanoclay-based anticorrosive coatings on magnesium alloy AZ91D

This study emphasizes on the evaluation and comparison of the anticorrosive properties of sol-gel coatings with and without inhibitor loaded nanocontainers.In this case,naturally available clay nanotubes(halloysite)were loaded with cationic corrosion inhibitors Ce 3+/Zr 4+.These nanocontainers were dispersed in hybrid organic-inorganic sol-gel matrix sol.Coating was applied on magnesium alloy AZ91D using the sols containing modified and unmodified nanocontainers employing the dip coating method and cured at 130℃for 1 h in air.Corrosion resistance of coated/uncoated substrates were analyzed using electrochemical impedance spectroscopy,potentiodynamic polarization and weight loss measurements after exposure to 3.5 wt%NaCl solution for varying time durations between 24 h to 120 h.Self-healing ability of coatings was evaluated by micro-Raman spectroscopy after 120 h exposure to 3.5 wt%NaCl solution.Coatings generated after dispersion of corrosion inhibitor loaded clay in hybrid sol-gel matrix have shown more promising corrosion resistance when compared to just the sol-gel matrix coatings,after prolonged exposure to corrosive environment.

Morphological Characteristics of (K, Na)-Rectoritefrom Zhongxiang Rectorite Deposit, Hubei, Central China

The morphological characteristics of the Zhongxiang （钟祥） rectorite have been studied using X-ray diffraction （XRD）, electron probe micro-analyzer （EPMA）, scanning electron microscopy （SEM）, atomic force microscope （AFM）, and high-resolution transmission electron microscopy （HRTEM）. The structural formula of the Zhongxiang rectorite is： （Na0.45K0.32Ca0.37Mg0.08）（Al3.78Fe0.11Ti0.10）[（Si6.22Al1.78）O20]（OH）4^＊nH2O. It should be confined to a regular interstratification of （K, Na）-mica and Ca-montmorillonite. SEM observations show that Zhongxiang rectorite occurs as platy and fold-shaped crystals, and mainly as extremely thin plates with thickness ranging from 0.4 to 0.05 μm and a smooth （001） surface. There are well-developed polygonal steps on the surfaces of some thick crystals, suggesting a layer-by-layer growth mechanism. AFM observations show a series of steps with a height of 2 nm on the platy particles, suggesting the stacking of 20 nm fundamental particles. Club-like or fiber-shaped halloysite is included in the platy crystals with their elongated dimension paralleling （001） of the platy crystals or crossing the （001） surface of the platy rectorite, indicating multi-stage crystallization and involvement of hydrothermal fluids. The Zhongxiang rectorite was generated by both layer-by-layer growth mechanism and dissolution and crystallization growth mechanism with multistages.

Microstructure and Photocatalytic Decomposition of Methylene Blue by TiO2-Mounted Halloysite, a Natural Tubular Mineral

On the basis of analysis of structure and properties, halloysite, a natural tubular mineral, was developed for an environmental treatment. TiO2 was mounted into halloysite by using hydrolysis of tetrabutyl titanate at room temperature. The adsorption and photocatalytic performance of halloysite and TiO2-mounted halloysite have been examined in methylene blue aqueous solution in the dark and under ultraviolet ray irradiation, respectively. Their performance of adsorption and photodecomposition was evaluated from the adsorbed and degraded amounts of methylene blue （MB）. Due to the mixture of adsorption and photodecomposition, the concentration of MB, organic pollution, in water decreased rapidly with TiO2-mounted halloysite powder, which is a faster reaction than that with halloysite-only adsorption. This new use of halloysite is leading to many interesting applications in the decomposition and elimination of various pollutants in air and water.

Release rate kinetics of corrosion inhibitor loaded halloysite nanotube-based anticorrosion coatings on magnesium alloy AZ91D

Halloysite nanotubes were used as nanocontainers to hold corrosion inhibitors such as Ce^(3+)-Zr^(4+),2-mercaptobenzothiazole and 8-hydroxyquinoline in their lumen.An acid assisted etching of the nanotubes was carried out with a view to increase the lumen diameter and thereby,increase the amount of loading of the corrosion inhibitor.The morphology of as-received and etched halloysite nanotubes was ob-served using TEM analysis.The loading of corrosion inhibitors was confirmed using SEM-EDS and BET analysis.Polymeric microcapsules were used as capping agents for the ends of the loaded HNTs following which,they were dispersed into a hybrid sol-gel silica matrix.Dip coating method was used to generate coatings on AZ91D substrates followed by heat treatment at 130℃ for 1 h.The release rate kinetics of corrosion inhibitors from as-received and etched nanotubes was investigated in buffer solutions of 3.5 wt%NaCl at different pH.The release mechanism of corrosion inhibitors from the HNT lumen was validated using various semi-empirical models.Coatings were also evaluated for their corrosion protection ability using electrochemical techniques after exposure to 3.5 wt%NaCl solution for 120 h.Coatings generated using Ce^(3+)-Zr^(4+)loaded into as-received halloysite nanotubes have shown more effective corrosion protection when compared to other corrosion inhibitors after 120 h exposure to the corrosive medium.

Ion shielding functional separator using halloysite containing a negative functional moiety for stability improvement of Li–S batteries

Lithium–sulfur batteries are one of the attractive next-generation energy storage systems owing to theienvironmental friendliness,low cost,and high specific energy densities.However,the low electrical conductivity of sulfur,shuttling of soluble intermediate polysulfides between electrodes,and low capacitretention have hampered their commercial use.To address these issues,we use a halloysitemodulated(H-M)separator in a lithium–sulfur battery to mitigate the shuttling problem.The H-M separator acts as a mutual Coulombic repulsion in lithium-sulfur batteries,thereby selectively permitting Lions and efficiently suppressing the transfer of undesired lithium polysulfides to the Li anode sideMoreover,the use of halloysite switches the surface of the separator from hydrophobic to hydrophilicconsequently improving the electrolyte wettability and adhesion between the separator and cathodeWhen sulfur-multi-walled carbon nanotube(S-MWCNT)composites are used as cathode active materialsa lithium–sulfur battery with an H-M separator exhibits first discharge and charge capacities of 1587 an1527 m Ah g-1,respectively.Moreover,there is a consistent capacity retention up to 100 cyclesAccordingly,our approach demonstrates an economical and easily accessible strategy for commercialization of lithium–sulfur batteries.

Enhancement of thermal stability and UV resistance of halloysite nanotubes using zinc oxide functionalization via a solvent-free approach

The aim of this study was to synthesize and evaluate the thermal properties and ultraviolet(UV)resistance of zinc oxide-functionalized halloysite nanotubes(HNT–ZnO).The HNT–ZnO was synthesized using a facile solvent-free route.The properties of the HNT–ZnO nanofillers were characterized using zeta-potential measurement,X-ray diffraction(XRD),field-emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),Fourier transform infrared spectroscopy(FTIR),and thermogravimetric analysis(TGA).The immobilization of ZnO nanoparticles onto HNT is feasible even at the lowest mass ratio of HNT/ZnO.The TGA results indicate that the thermal stability of the HNT–ZnO nanofillers is higher than that of the HNT.Furthermore,UV?Vis diffuse reflectance spectroscopy(UV-DRS)results show that the HNT–ZnO achieve a total reflectance as high as approximately 87.5%in the UV region,as compare with 66.9%for the HNT.In summary,the immobilization of ZnO onto HNT is a viable approach for increasing the thermal stability and improving the UV shielding of HNT.

MORPHOLOGY,INTERFACIAL INTERACTION AND PROPERTIES OF STYRENE-BUTADIENE RUBBER/MODIFIED HALLOYSITE NANOTUBE NANOCOMPOSITES

A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier.The structure,morphology and mechanical properties of SBR/m-HNT nanocomposites,especially the interfacial interactions,were investigated.SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix at ...

Electroless deposition of Ni on template of halloysite and its magnetic property

Halloysite template, a ceramic substrate, is of a hollow cylindric structure, on which the fine Pd nanoparticles are uniformly formed by the reduction of palldate chloride to initiate electroless deposition. The electroless deposition of Ni is catalyzed by the Pd particles, which results in a uniform layer of Ni-P alloy on halloysite. The alloy is of a nanocrystalline structure, of which the average diameter is about 6 nm. After being heat-treated at 400 ℃, it contains both Ni and Ni12P5 crystal, meanwhile, the Ni crystal gets larger with an average size of 51.9 nm.The content of phosphorous in the Ni layer has a great influence on crystal structure. The metallized halloysite has a higher inherent coercive force, and a much lower saturation magnetization in its as-plated state, while after heattreatment, the inherent coercive force decreases drastically. These magnetic properties have great relationship with the superparamagnetism of Ni nanocrystalline and the stress anisotropy in Ni layer.

Experimental Study on Adsorption of Rare Earth Elements on Kaolinite and Halloysite

1 Introduction The weathered crust rare earth deposits is one of the most significant rare earth deposits,which are mostly distributed in southern China,especially in the south of Jiangxi province(Chi et al.,2007).The compositions of these deposits,which are weathered from igneous rocks such as granite through biological,physical or chemical

Graphene-intercalated HNTs for Reinforcing PTFE

The preparation of graphene(GN)and graphene-intercalated halloysite nanotubes(HNTs)to form nanomaterials was achieved by using HNTs template.As a promising application,a series of the polytetrafluoroethylene(PTFE)nanocomposite filled with GN and GN/HNTs at different mass fractions were prepared.The mechanical and friction properties of PTFE nanocomposites depending on the mass fraction of graphene-intercalated HNTs(GN/HNTs)were intensively investigated.The comparison between the effects of GN and GN/HNTs serving as fillers on properties of PTFE was presented.The results showed that in terms of enhancing the tensile strength of PTFE,the enhancement effect of GN is superior to GN/HNTs,and in terms of the elongation at break,the GN/HNTs filler could reserve more toughness than GN.The Young’s modulus of the GN/HNTs incorporated into PTFE is about 1.9 times larger than pure PTFE,and is superior to GN/HNTs.The friction coefficient of PTFE nanocomposites filled with GN and GN/HNTs was slightly higher than pure PTFE and the latter was lower than the former.The volume wear rate of PTFE nanocomposites filled with GN/HNTs was obviously lower than the case with GN,which exhibited the better wear resistance of GN/HNTs used as filler.

Development of Sulfuric Acid Speleogenetic Deposits within Cavernous Middle Eocene Beds:Inference on Hydrocarbon Gas Seepages,Giza Pyramids Plateau,Egypt

Development of sulfuric acid speleogenetic mineral deposits within cavernous middle Eocene beds of the Pyramids plateau is linked to hydrocarbon gas seepages.The work carried out field observations,binocular,polarizing,scanning and transmitted electron microscopy investigation,X-ray diffraction and X-ray fluorescence analyses.The morphological and petrographic features and chemical composition of the studied mineral deposits reveal a hypogene sulfuric acid speleogenesis.A model comprised of the following stages can be used to explain the presence of these features.(1)Ascent of hydrogen sulfide(H_(2)S)gas associated with hydrocarbon seepages from the Cretaceous reservoirs under reducing conditions followed by oxidation to sulfuric acid(H_(2)SO_(4)),(2)descent of carbonic acid(H_(2)CO_(3))-rich solution generated from surface sources,(3)reaction of H_(2)SO_(4)and H_(2)CO_(3)with the calcareous and argillaceous host rocks,(4)formation of H_(2)SO_(4)speleogenetic by-products represented by natroalunite,aluminium-phosphate-sulfate,hydrated halloysite and Fe/Mn oxides within the replacive gypsum,and(5)subsequent stresses due to the formation of nearby stratiform cavities gave rise to the development of fractures/veinlets filled with displacive fibrous satinspar gypsum.The study sets the paleokarst features of the Giza Pyramids plateau within a hypogene sulfuric acid karst system developed by the action of groundwater containing H_(2)S,H_(2)SO_(4)and H_(2)CO_(3).

Synergistic Effect of Halloyosite Nanotube and Nanocellulose on Thermal and Mechanical Properties of Poly(Ethylmethacrylate-co-Acrylonitrile)Bionanocomposites

This work reports a comprehensive study on poly(Ethylmethacrylateco-Acrylonitrile)Poly(EMA-AN)nanocomposites reinforced with a hybrid mixture of nanoreiforcements based on nanocrystals of cellulose(NCC)(1 or 5%wt)and halloysite nanotubes(HNTs)(1 or 5%wt).The morphology,thermal and mechanical properties of these nanocomposites were characterized.Homogeneous dispersion of the nanofillers has been shown by scanning electron microscopy.A significant increase of the rubbery modulus and glass transition temperature were obtained upon filler addition,due to the reduction of mobility of the matrix macromolecular chains.On the other hand,compared with the neat Poly(EMAAN),the storage modulus of the nanocomposites increased by a factor 38 when adding 5 wt%NCC and by 17 for the same concentration of HNTs.mechanical properties of ternary nanocomposites were furthers increased resulting from a synergistic effect of these two nanofillers.

Effect of preparation method on halloysite supported cobalt catalysts for Fischer-Tropsch synthesis

Novel cobalt Fischer-Tropsch synthesis （FTS） catalysts were prepared from natural halloysite nanotubes （HNT） by double-solvent and wet- impregnation methods, and characterized by TEM, XRD, TPR and N2 adsorption-desorption. Comparing with the catalyst prepared by wet- impregnation method, the catalyst prepared by double-solvent method reduces Co3O4 particle migration and agglomeration due to size-induced effect, thus showing higher catalytic activity for Fischer-Tropsch synthesis.

Environmental Stress Cracking Resistance of Halloysite Nanoclay-Polyester Nanocomposites

The environmental stress cracking resistance of halloysite nanoclay-polyester nanocomposites was investigated using fracture mechanics approach. The incorporation of halloysite nanoclay was found to improve the environmental stress cracking resistance of the nano-composites. The storage modulus of nano-composites measured by dynamic mechanical analysis increased remarkably as a function of halloysite nanoclay content. At 0.7 wt% nanoclay, the Tg improved from 72°C to 76°C. The fracture toughness increased up to 33% and time to failure improved 155% with the addition of 0.7 wt% of halloysite nanoclay. The maximum microhardness was found 119% higher for the same nano-filler concentration compared to monolithic polyester. The reinforcement with 1 wt% showed lower fracture toughness due to agglomerations of nanoclay which act as flaws. The presence of agglomerates weakened the bond between nano-particles and matrix hence reduces the environmental stress cracking resistance by halloysite nanoclay reinforcement.

Transport Properties of Novel Hybrid Cation-Exchange Membranes on the Base of MF-4SC and Halloysite Nanotubes

The diffusion permeability through new hybrid materials based on a Nafion-type membrane (MF- 4SC) and nanotubes of halloysite is investigated using the Nernst-Planck approach. A method of quantitative evaluation of physicochemical parameters (averaged and individual diffusion coefficients and averaged distribution coefficients of ion pairs in the membrane) of system “electrolyte solution—ion-exchange membrane—water”, which was proposed earlier, is further developed. The parameters of hybrid membranes on the base of MF-4SC and nanotubes of halloysite (5% wt and 8% wt) are obtained from experimental data on diffusion permeability of NaCl solutions using theoretical calculations. New model of three-layer membrane system can be used for refining calculated results with taking into account both diffusive layers. It is shown that adding of halloysite nanotubes into the membrane volume noticeably affects exchange capacity as well as structural and transport characteristics of original perfluorinated membranes. Hybrid membranes on the base of MF-4SC and halloysite nanotubes can be used in fuel cells and catalysis.

Mechanical and Crystalline Behavior of Polymeric Nanocomposites in Presence of Natural Clay

Fabrication of nanocomposites from immiscible polymer blend system has been represented in this work. A new type of natural clay named Halloysite nanotubes (HNTs) are modified by Polyethyleneimine (PEI) and these PEI grafted HNTs are incorporated into the immiscible blend system during melt mixing process to prepare halloysite based nanocomposites. Fourier Transform Infrared Spectroscopy (FTIR) study confirms the formation of PEI grafted HNTs. The nanocomposites are characterized by SEM for morphological study and, the dispersion manners of nanoclays by Transmission Electron Microscopy (TEM). Storage modulus is studied by Dynamic mechanical thermal analysis (DMTA) instrument. The tensile measurement explored better tensile property of nanocomposites as compared to the virgin blend. XRD is performed to determine the crystalline behavior of the nanocomposites as well as for blend. The above investigations reveal that the HNTs act as reinforcing as well as nucleating agent in the blend system.

Implementation of a Simulation Model of the Controlled Release of Molecular Species from Halloysite Nanotubes

In this work a three-dimensional, time-quantified Monte Carlo model that efficiently describes diffusion through and from nanotubes is implemented. Controlled delivery from Halloysite Nano-tubes (HNT) is modeled based on interactions between the HNT’s inner wall and the nanoparticles (NPs) and among NPs themselves. The model was validated using published experimental data. The validated model is then used to study the effect of multiples parameter like HNT diameter and length, particle charge, and ambient temperature on the release of encapsulated NPs. The results show that release profiles depend on the size distribution of the HNT batch used for the experiment, as delivery is sensitive to HNT lumen and length. A very good agreement with the experiment is observed when a weighted average release profile is compared to the experimental profile. Although the NP dynamics is temperature-dependent, the effect is minimum within the range of temperatures relevant to biomedical applications, but will be relevant for other applications at temperatures significantly different from room temperature. This model can be used to predict the best conditions for a particular delivery need.