Dispersion Of Halloysite Nanotubes Research Articles

A self-healing crosslinked-xanthan gum/soy protein based film containing halloysite nanotube and propolis with antibacterial and antioxidant activity for wound healing

Traumatic multidrug-resistant bacterial infections are the most threat to wound healing. Lower extremity wounds under diabetic conditions display a significant delay during the healing process. To overcome these challenges, the utilization of protein-based nanocomposite dressings is crucial in implementing a successful regenerative medicine approach. These dressings hold significant potential as polymer scaffolds, allowing them to mimic the properties of the extracellular matrix (ECM). So, the objective of this study was to develop a nanocomposite film using dialdehyde-xanthan gum/soy protein isolate incorporated with propolis (PP) and halloysite nanotubes (HNTs) (DXG-SPI/PP/HNTs). In this protein-polysaccharide hybrid system, the self-healing capability was demonstrated through Schiff bonds, providing a favorable environment for cell encapsulation in the field of tissue engineering. To improve the properties of the DXG-SPI film, the incorporation of polyphenols found in PP, particularly flavonoids, is proposed. The synthesized films were subjected to investigations regarding degradation, degree of swelling, and mechanical characteristics. Additionally, halloysite nanotubes (HNTs) were introduced into the DXG-SPI/PP nanocomposite films as a reinforcing filler with varying concentrations of 3 %, 5 %, and 7 % by weight. The scanning electron microscope (SEM) analysis confirmed the proper embedding and dispersion of HNTs onto the DXG-SPI/PP nanocomposite films, leading to functional interfacial interactions. The structure and crystallinity of the synthesized nanocomposite films were characterized using Fourier Transform Infrared Spectrometry (FTIR) and X-ray diffraction (XRD), respectively.Moreover, the developed DXG-SPI/PP/HNTs nanocomposite films significantly improved cell growth of NIH-3T3 fibroblast cells in the presence of PP and HNTs, indicating their cytocompatibility. The antibacterial activity of the nanocomposite was evaluated against Escherichia coli (E. Coli) and Staphylococcus aureus (S. Aureus), which are commonly associated with wound infections. Overall, our findings suggest that the synthesis of DXG-SPI/PP/HNTs nanocomposite scaffolds holds great promise as a clinically relevant biomaterial and exhibits strong potential for numerous challenging biomedical applications.

Eco-friendly flame-retardant bamboo fiber/polypropylene composite based on the immobilization of halloysite nanotubes by tannic acid-Fe3+ complex

Bamboo fibers (BF), as an important sustainable natural material, are becoming a hot alternative to synthetic fibers for the reinforcement of polypropylene (PP)-based composites. However, the weak interfacial compatibility between BF and PP as matrix and their inherent flammability limit the practical application of BF/PP composites (BPC). Here, a fire-safe BPC was fabricated by constructing flame-retardant interfacial layers containing tannic acid (TA)-Fe3+ complex and halloysite nanotubes (HNTs) on the fiber matrix followed by a hot-pressing process. The results showed that the interfacial chelating of TA with Fe3+ improved the dispersion of HNTs on the fibers and the interfacial interactions within the fiber matrix, resulting in the as-fabricated composite with significantly improved mechanical properties and water resistance. In addition, the flame-retardant composite exhibited higher thermal stability and enhanced residual char content. Moreover, the composite possessed significant flame-retardant performances with a reduction of 23.75 % in the total heat release and 32.44 % in the total smoke production, respectively, owing to the flame retarding in gaseous phase and condensed phase of TA-Fe3+@HNTs layers. This work offers a green and eco-friendly strategy to address the inherent problems of BPC material in terms of fire safety and interfacial compatibility, thus broadening their applications in the automotive interior and construction industries.

Formation and Application of Polymer Spherulite-like Patterns of Halloysite Nanotubes by Evaporation-Induced Self-Assembly.

Halloysite nanotubes (HNTs) are one-dimensional clay nanomaterials featuring distinct tubular structures and unique surface charges. HNTs can readily form ordered assembly structures under specific conditions, which shows significant potential applications in optical and biological fields. In this study, sodium hexametaphosphate (SHMP) was employed as a stabilizer to prepare polymer spherulite-like patterns via the evaporation-induced self-assembly (EISA) technique. The incorporation of SHMP enhanced the repulsion force among the nanotubes and the surface potential, which facilitated the orderly deposition of HNTs. The influence of HNT concentration, SHMP concentration, drying temperature, and substrate on the polymer spherulites-like pattern has been investigated in detail. The optimal conditions were 10 wt % HNT dispersion, 0.6 wt % SHMP concentration, 30 °C as drying temperature, and glass substrates. In addition, by changing the droplet volume and shape of the three-phase contact line, patterns of different sizes and shapes can be achieved. Bovine serum albumin or metal salt compounds were incorporated into the dispersion of SHMP-modified HNTs, which altered the charge and the self-assembled patterns with different area ratios. Thus, this technology can be utilized for the analysis and comparison of protein and metal ion concentration accurately. This study creates the correlation between the structural parameters and the preparation process involved in creating polymer spherulite-like patterns of modified HNTs and offers fresh insights into potential applications for the self-assembly of HNT droplets in the realms of anticounterfeiting and solution concentration analysis.

Lap shear properties of CF/PEKK composites through nanoparticle-enhanced adhesive joints

This study investigates the effects of incorporating halloysite nanotubes (HNTs) into polyetherimide (PEI) adhesive for carbon fiber/polyetherketoneketone (CF/PEKK) composite joints. The CF/PEKK substrate is fabricated through an oven consolidation process, while PEI adhesive films with varying HNTs loadings (0.5, 1 and 3[Formula: see text]wt.%) are prepared using solvent casting with [Formula: see text]-butyrolactone. Homogeneous dispersion of HNTs in PEI is achieved through magnetic stirring and IR heating. The resulting film is hot pressed to form a 100[Formula: see text][Formula: see text]m thick film, and adhesive lap shear joint specimens are manufactured through oven consolidation. Morphology and dispersion of HNTs in PEI are analyzed using SEM and EDS, revealing favorable dispersion at 0.5[Formula: see text]wt.% HNTs and aggregation at higher loadings. Differential scanning calorimetry (DSC) is employed to study the glass transition temperature (Tg) of PEI, showing decreased Tg for solvent-cast PEI and increased Tg with HNTs incorporation. This increase is attributed to the constrained mobility of polymer chains due to HNTs’ influence. Lap shear strength (LSS) is evaluated, demonstrating enhancement with HNTs incorporation: 0.5[Formula: see text]wt.% HNTs (+12.5%) > 1[Formula: see text]wt.% HNTs (+8.33%) > Pure PEI > 3[Formula: see text]wt.% HNTs (−12.5%). The study attributes this enhancement to HNTs’ reinforcement and chemical interactions with PEKK. Aggregation tendencies at 3[Formula: see text]wt.% HNTs lead to decreased LSS. SEM-EDS analysis of fractured specimens indicates a multifaceted bonding joint interface involving PEKK, PEI and HNTs. CF/PEKK composites show adhesive, cohesive and adherend failure modes, with adherend failure being dominant. Notably, fabric-like textures and plastic deformations in PEI with 0.5[Formula: see text]wt.% HNTs contribute to enhanced LSS, while higher HNTs content leads to cohesive failure due to aggregation. This study provides insights into optimizing composite adhesive systems by harnessing nanotube reinforcement and controlling dispersion, thereby influencing interfacial strength.

Preparation and Characterization of Polydopamine-Modified Halloysite Nanotubes and Their Effect on a Natural Rubber, Chloroprene Rubber and Chloro-Isobutylene-Isoprene Rubber Blend

The superior physical and mechanical performances of halloysite nanotubes (HNTs) make them ideal fillers for rubber reinforcement. However, due to the abundant hydroxyl groups on their surface, they are highly polar and have poor compatibility with polymers, making it difficult for them to disperse uniformly in polymers, thus limiting their application in rubber composites to a certain extent. In this paper, noncovalently modified HNTs filled with a natural rubber/chloroprene rubber/chloro-isobutylene-isoprene rubber (NR/CR/CIIR) blend system, using polydopamine(PDA) as a surface modifier, was investigated. and a green and high-performance PDA/HNTs/NR/CR/CIIR composite was prepared by mechanical blending. Transmission electron microscopy (TEM) showed that the original HNTs had a hollow, multi-walled nanotube structure, and the outer surface of the PDA-modified halloysite nanotubes(PDA/HNTs)showed an obvious cladding layer. X-ray diffraction indicated that the modification experiments did not damage the halloysite crystal structure; the modifier only interacted on the outer surface of the HNTs. Zeta potential and thermogravimetric analysis (TGA) further indicated the presence of interfacial interactions between PDA and HNTs, suggesting that PDA was successfully grafted to the surface of HNTs. In addition, the effects of PDA/HNTs on the mechanical properties, vulcanization properties and Rubber Process Analyzer (RPA analysis) of the NR/CR/CIIR blend were also investigated. The dispersion of HNTs in the NR/CR/CIIR blend was enhanced by the adsorption of PDA on the HNTs surface by non-covalent bonds, and the comprehensive properties of the composites were improved.

The Effect of Cu2+ and Pb2+ in the Feed Solution on the Water and Reverse Solute Fluxes in the Forward Osmosis (FO) Process Using Nanofiltration (NF) Membranes

The application of nanofiltration (NF) membranes in the forward osmosis (FO) process to remove heavy metal ions from wastewater is an emerging concept. Unlike NF, FO does not require an external driving force. Although the product, a dilute draw solution, must further be processed by NF to produce pure water and reconcentrate a draw solution, the feed to that NF process is “clean”, which minimizes membrane fouling. This paper examines the role of Cu2+ and Pb2+ in the feed solution on the water and the reverse solute fluxes in FO process using novel thin film nanocomposite (TFN) NF membranes. The TFN membranes were fabricated by in situ interfacial polymerization of piperazine (PIP) and 1,3,5-benzenetricarbonyl trichloride (TMC) containing different amounts of dispersed halloysite nanotubes (HNTs) nanoparticles functionalized with the first generation of poly(amidoamine) (PAMAM) dendrimers. The presence of Cu2+ and Pb2+ in the feed solution decreased the reverse flux of MgCl2 by at least 2.5 times compared to the experiments with pure water as a feed. Simultaneously, the water flux also increased. The corresponding rejections of Cu2+ and Pb2+ in the FO process ranged from 94.5% to 98.1%.

Halloysite nanotubes modified poly(vinylidenefluoride-co-hexafluoropropylene)-based polymer-in-salt electrolyte to achieve high-performance Li metal batteries

Solid-state Li metal batteries (SSLMBs) are one of the most promising energy storage devices, as they offer high energy density and improved safety compared to conventional Li-ion batteries. However, the large-scale application of SSLMBs at room temperature is restricted by the main challenges such as low ionic conductivity and poor cyclic performance. Herein, a composed polymer-in-salt electrolyte (CPISE) is fabricated, which is composed of polyvinylidene vinylidene hexafluoropropene (PVDF-HFP) and high-concentration Li bis(trifluoromethanesulphonyl)imide (LiTFSI), reinforced with natural halloysite nanotubes (HNTs). The High concentration of LiTFSI and introduced HNTs synergized with PVDF-HFP to provide more various Li+ transport pathways. Additionally, the backbones of the uniform dispersion of HNTs in the CPISE effectively boosts the physicochemical nature of the CPISE. As a result, the prepared CPISE achieves excellent mechanical strength, high ionic conductivity (1.23*10-3 S cm−1) and high Li+ transference number (0.57) at room temperature. Consequently, in existence of the CPISE, the Li symmetric cell cycles stably beyond 800 h at 0.15 mA cm−2 and the LiFePO4/Li cell displays impressive cyclic performance with capacity retention of 79% after 1000 cycles at 30 °C. Furthermore, the superiority and the functional mechanism of the CPISE are discovered in detail. This work provides a promising strategy for the development of high-performance SSMLBs at room temperature.

Microstructure–properties relationship in ethylene-propylene diene monomer (EPDM)/nitrile butadiene rubber (NBR)/halloysite nanotubes (HNTs) nanocomposites

AbstractStructure–properties relationship in complex rubber nanocomposites is a key for enlarging the performance window. Herein, halloysite nanotubes (HNTs) are added at variable content to ethylene-propylene diene monomer (EPDM)/nitrile butadiene rubber (NBR) rubber blends compatibilized with maleic anhydride grafted HNTs to evaluate cure characteristics, along with microstructure, and mechanical and swelling behavior. The crosslinking rate increased by HNTs loading, but the scorch time decreased. Moreover, a 45% rise in tensile strength was observed for systems containing 10 wt% HNTs. SEM and TEM micrographs revealed a rough fracture surface with proper dispersion of HNT within EPDM/NBR. The modulus of EPDM/NBR/HNTs nanocomposites is theoretically estimated by modified Kolarik model, demonstrating a good agreement with experimental value. Dynamic mechanical thermal analysis (DMTA) revealed a higher storage modulus up to 2.27 GPa with the introduction of HNTs into EPDM/NBR compound. Correspondingly, lower solvent uptake (decreased by 38%) is reported. Thermogravimetric analysis (TGA) revealed higher thermal stability for highly-loaded systems.

Halloysite Nanotube-Based Pesticide Formulations with Enhanced Rain Erosion Resistance, Foliar Adhesion, and Insecticidal Effect.

The incorporation of green and sustainable nanomaterials in pesticide formation is an effective method to lower the use of conventional pesticides without adverse effects on productivity. Here pesticide Pickering emulsions stabilized by halloysite nanotubes (HNTs) were developed for low cost, less environmental pollution, low toxic effects, and better emulsion stability. HNTs were added to chlorantraniliprole (CAP) emulsions, and good stability was exhibited due to the adsorption and aggregation of HNTs at the interface of CAP oil droplets, forming a three-dimensional network structure that prevented the emulsion from aggregation. In addition, Spodoptera frugiperda was used as a pest model and corn was used as a plant model to explore the washout resistance, insecticidal effect, and biological safety of HNTs-CAP emulsion. After spraying emulsion on corn leaves and washing for 10 min, the HNTs-CAP emulsion (5 wt % HNTs) pesticide residue rate was 2.7 times that of pristine CAP emulsion. When the HNT dispersion concentration was 2 wt %, the larva mortality was 83%, which was 1.5 times that of the CAP emulsion group. These results demonstrated that HNTs-CAP emulsion showed good foliar adhesion, rainfall resistance, and insecticidal effect. The tubular clay-based nanopesticide formulations show potential applications in the control of crop pests with modern agriculture technology.

Advanced Kolarik model for the modulus of a nanocomposite system reinforced by halloysite nanotubes and interphase zone

AbstractIn the current article, Kolarik model is progressed for the tensile modulus of a polymeric system containing dispersed halloysite nanotubes (HNT) and adjacent interphase section. The progressive model correlates the nanocomposite's modulus to HNT concentration (volume fraction and weight percentage), the extents of HNT and nearby interphase section in addition to the densities of polymer medium and HNT. The productions of the progressive model are linked to the tentative results and the influences of all variables on the modulus of system are justified. The modulus of system reduces as HNT radius increases, but HNT weight percentage directly controls the nanocomposite's modulus. The modulus of samples maximizes by 47% by the deepest interphase section of 20 nm establishing a straight link among nanocomposite's modulus and interphase thickness. The increment of polymer matrix density improves the modulus of samples, but there is an opposite relation between the modulus of system and HNT density. Furthermore, the calculations exactly match to the experimental facts of numerous examples representing the accurateness of the progressed model.

Surface decoration of Halloysite nanotubes with POSS for fire-safe thermoplastic polyurethane nanocomposites

• POSS modified HNTs were synthesized successfully by using a silane agent as a chemical bridge. • The POSS in combination with HNTs endows TPU with excellent flame retardancy without scarifying the mechanical property. • The incorporation of 2 wt% HNTs-POSS into TPU could effectively reduce the peak of the peak of CO production rate and total smoke release during combustion. Halloysite nanotubes (HNTs) have been considered as a promising flame retardant fillers for polymers. In this work, the polyhedral oligomericsilsesquioxane (POSS) containing amino group was covalently grafted on the surface of HNTs with 3-(2,3-epoxypropoxy)propytrimethoxysilane as a chemical bridge. The POSS modified HNTs (HNTs-POSS) dispersed uniformly in the thermoplastic polyurethane (TPU) matrix and endowed TPU nanocomposites with enhanced tensile properties and fire safety. Cone calorimeter tests revealed that the introduction of 2 wt% HNTs-POSS to TPU matrix remarkably reduced the peak of heat release rate (PHRR) and total heat release (THR) by 60.0% and 18.3%, respectively. In addition, the peak CO production rate and total smoke release (TSR) could be significantly suppressed by the addition of HNTs-POSS. The well dispersed HNTs in combination with the ceramified silicon network from the thermal decomposition of POSS contributed to the formation of a continuous and compact char layer, exhibiting a tortuous effect by inhibiting heat diffusion and evaporation of volatile gaseous. In addition, the released crystal water from HNTs could dilute the combustible volatiles and then decline the combustion intensity. The tensile tests demonstrated that introduction of 2 wt% HNTs-POSS would enhance the maximum stress of TPU nanocomposite with a slight decrease of elongation at break. The combination of HNTs and POSS through the construction of effective interfacial interactions provides a feasible way to effectively enhance the fire safety of TPU nanocomposites without scarifying ductility.

Architected poly(lactic acid)/poly(\u03b5-caprolactone)/halloysite nanotube composite scaffolds enabled by 3D printing for biomedical applications

Herein, we report the physicochemical, thermal, mechanical and biological characteristics, including bioactivity, biodegradation and cytocompatibility of additive manufacturing-enabled novel nanocomposite scaffolds. The scaffolds comprise a blend of polylactic acid (PLA) and poly-ε-caprolactone (PCL) reinforced with halloysite nanotubes (HNTs). The nanoengineered filaments were developed by melt blending, and the nanocomposite scaffolds were manufactured by fused filament fabrication. Uniform dispersion of HNTs in the PLA/PCL blend is revealed via scanning electron microscopy. Mechanical property loss due to the addition of PCL to realize a suitable biodegradation rate of PLA was fully recovered by the addition of HNTs. Bioactivity, as revealed by the fraction of apatite growth quantified from XRD analysis, was 5.4, 6.3, 6.8 and 7.1% for PLA, 3, 5 and 7 wt% HNT in PLA/PCL blend, respectively, evidencing enhancement in the bioactivity. The degradation rate, in terms of weight loss, was reduced from 4.6% (PLA) to 1.3% (PLA/PCL) upon addition of PCL, which gradually increased to 4.4% by the addition of HNTs (at 7 wt% HNT). The results suggest that the biodegradation rate, mechanical properties and biological characteristics, including cytocompatibility and cell adhesion, of the 3D printed, microarchitected PLA/PCL/HNT composite scaffolds can be tuned by an appropriate combination of HNT and PCL content in the PLA matrix, demonstrating their promise for bone replacement and regeneration applications.Graphical abstract

Dispersion analysis of nanofillers and its relationship to the properties of the nanocomposites

The dispersion and distribution characteristics of the reinforcements are the key reasons that influence the mechanical properties of the nanocomposites. In this paper, the dispersion and distribution analysis of nanofillers in a representative polymer is performed and the results are correlated to the crystalline and mechanical properties of the nanocomposite. The nanocomposite used in the present study is Elvaloy®4924 (EVACO)/halloysite nanotubes (HNTs) composite. The dispersion of halloysite nanotubes in the EVACO matrix is recorded as aluminum elemental maps obtained from energy dispersive spectroscopy (EDS). The dispersion and distribution of fillers in the composite are quantified using an image processing technique and it is correlated to the crystalline and tensile properties of the composites. The better dispersion and distribution of HNTs at 1wt.% filler loading resulted in a remarkable improvement in the crystallinity of the composite, which is measured by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The tensile strength was highest for composites loaded with 1 wt.% filler, and the strength decayed as the loading was further increased. Agglomeration of halloysite nanotubes and polymer-filler debonding was the major reason behind the reduction in tensile strength with filler loading, as observed in the scanning electron micrographs of the fractured surfaces.

Tunable coffee-ring formation of halloysite nanotubes by evaporating sessile drops.

Halloysite nanotubes (HNTs) are one-dimensional clay nanomaterials with a length of 200-1000 nm and a diameter of ∼50 nm. Understanding the self-assembly behavior of such unique nanoparticles is important to develop their applications in functional devices. In this study, the "coffee-ring" patterns of HNTs are investigated which are formed by evaporation of the sessile droplets of HNT aqueous dispersion on different substrates. The coffee-ring pattern with various dimensions was characterized using a polarizing microscope (POM), a scanning electron microscope (SEM), and a 3D optical profilometer. The diameter, height, and area of the coffee-ring patterns depend on the concentration of HNT dispersion, the droplet volume, and surface wettability. POM and SEM results suggested that the nanotubes were highly ordered in the edge and the middle of the coffee-ring. The coffee-ring effect of HNTs could be suppressed by increasing the evaporation temperature of substrates or adding polymer additives. In addition, multiple-ring patterns consistent with protein rings surrounding HNT rings were formed, which can be utilized to detect the presence of proteins in biological samples. This work illustrated the relationship between the formation of coffee-ring patterns and the experimental conditions, which provided an additional research chance and allowed application development for HNTs using the liquid droplet self-assembly.

Alginate-Halloysite Nanocomposite Aerogel: Preparation, Structure, and Oil/Water Separation Applications.

Environmental remediation using green approaches for addressing various pollution-related issues, especially water pollution, is in high demand. Here, we designed an environmentally friendly, low-cost, and stable sodium alginate–halloysite clay composite aerogel (SAHA) for oil/water separation via a two-step synthesis procedure, including ionic crosslinking and freeze-drying. The as-prepared SAHA aerogels were characterized in detail by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and Fourier transformation infrared (FT-IR) spectroscopy. Characterization of the SAHA aerogels revealed a three-dimensional porous microstructure with uniformly dispersed halloysite nanotubes (HA) within the alginate matrix. The elemental composition of the hydrogels investigated using energy dispersive X-ray spectrometry (EDX) revealed the presence of minerals, such as magnesium, sodium, aluminum, and silicon in the SAHA aerogels. The presence of a hydrophilic alginate matrix combined with these unique morphological characteristics resulted in SAHA aerogels with underwater oleophobicity and excellent oil/water separation efficiency (up to 99.7%). The ease of fabrication, excellent oil/water separation, and multiple performances make the SAHA aerogel an interesting candidate for practical applications in water recycling.

Effect of chain extender on structural and mechanical properties of poly(butylene succinate‐co‐adipate)/halloysite nanotube bionanocomposites

AbstractBionanocomposites comprising poly(butylene succinate‐co‐adipate) (PBSA) and halloysite nanotubes (HNTs) were fabricated via melt extrusion using different HNT loadings. These nanocomposites were characterized through Fourier transfer infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and mechanical, thermal, and rheological tests. Adding a chain extender (CE) ensured homogeneous dispersion of HNTs in the PBSA matrix because the epoxy‐based CE and HNTs reacted with the carboxyl groups of PBSA, leading to effective interfacial interactions between the matrix and reinforcing filler. Differential scanning calorimetry results revealed that HNTs had a nucleating effect on PBSA, thereby increasing the crystallization of PBSA and percentage crystallinity of the composites. Nevertheless, the CE did not cause any change in the crystallinity of the nanocomposites. Further, the thermal stability of PBSA without and with the CE reduced, depending on the HNT loading. The HNTs and CE also increased the melt strength of PBSA. Additionally, HNTs and CE enhanced the mechanical properties owing to the increased molecular weight and formation of long‐chain branched structures.

Detailed investigation of the reinforcing effect of halloysite nanotubes-filled epoxidized natural rubber

The properties of rubber composite depend on the compatibility between rubber and filler. This is specifically of concern when preparing composites with very different polarities of the rubber matrix and the filler. Natural rubber (NR) and halloysite nanotubes (HNT) are one of the examples of the incompatible system. Epoxidized natural rubber (ENR) was used as the main matrix, with halloysite nanotubes (HNT) as a filler, in order to obtain composites with improved performance. ENR was prepared in house using performic acid with a controlled reaction time to obtain samples with mole epoxide levels from 10 to 40 mol%. Varying the mole epoxide levels was expected to optimize the formulation for this rubber composite. The compounds obtained were then investigated for the rubber–filler interactions of the ENR and HNT. By increasing the mole percentage of epoxide, the scorch and cure times were decreased while the maximum torque and torque differences increased. The ENR at 40 mol% epoxide exhibited least filler–filler interaction as shown from the Payne effect together with the supporting result from FTIR spectrum. However, this ENR compound did not yield the optimum tensile strength due to the constraint on the rubber–filler interaction. This study revealed that the use of ENR with a suitable mole percent of epoxide can dramatically reduce the filler–filler interaction and hence enhance the dispersion of HNT, which was seen from SEM micrographs, and resulted in enhancement of the mechanical and dynamical properties of the composites.

Rational Design of Halloysite Surface Chemistry for High Performance Nanotube-Thin Film Nanocomposite Gas Separation Membranes.

The interfacial region has a critical role in determining the gas separation properties of nanofiller-containing membranes. However, the effects of surface chemistry of nanofillers on gas separation performance of thin film nanocomposite (TFN) membranes, prepared by the interfacial polymerization method, have been rarely studied in depth. In this work, pristine and three differently surface-modified halloysite nanotubes (HNTs), by non- (SHNT), moderately (ASHNT), or highly CO2-philic (SFHNT) agents, are embedded in the polyamide top layer of thin film nanocomposite (TFN) membranes for CO2/N2 and CO2/CH4 separations. Trimethoxyoctyl silane, 3-(2-aminoethylaminopropyl)trimethoxysilane, and poly(styrenesulfonic acid) are used as modifying agents to quantitatively investigate the effects of interfacial interactions between the polyamide and HNTs on the gas permeation of TFNs. This allows us to provide an interfacial design strategy to fabricate high-performance gas separation membranes. Pure gas permeations conducted on the TFNs at the feed gas pressure of 10 bar showed that CO2 permeance and CO2/N2 and CO2/CH4 selectivities were increased by 145%, 130%, and 108%, respectively, after addition of 0.05 w/v% of sulfonated HNTs. The experimental gas permeations through all TFNs/HNTs, except TFNs/SFHNTs, agree well with predictions of a recently developed model, which suggests the importance of considering the neglected role of CO2 interactions with the HNT/polyamide interface in the model. These results unambiguously proved that designing the interfacial layer thickness in the nanotube-containing membranes is an effective approach to tuning the gas separation properties. The results show that the dispersion of HNTs in the polyamide top layer and the experimental CO2/gas selectivity was increased with increasing interfacial thickness, aint, upon surface modification. Moreover, it is quantitatively demonstrated that the thickness of the interfacial layer between the filler and polymer matrix is a function of gas pressure applied on the membrane.

Halloysite nanotubes-based supercapacitor: preparation using sonochemical approach and its electrochemical performance

In this study, halloysite nanotubes polyaniline (HNT-PANI) nanocomposite was synthesized by using an ultrasound-assisted method. Because of high conductivity, ease of synthesis, low cost, nanosize tubular structure and improved structural/electrochemical properties, HNT-PANI had been used for the electrode fabrication of a supercapacitor. The dispersion of halloysite nanotubes in polyaniline was prepared by following an ultrasound approach. The structural and morphological studies of the HNT-PANI nanocomposite were investigated by X-ray diffraction, Fourier Transform Infrared Spectroscopy, Raman and transmission electron microscopy. The length of the halloysite nanotubes varied from 200 to 1000 nm and the composite nanoparticles possessed tubular hallow shaped structure. The electrochemical performance of the HNT-PANI nanocomposite electrode was analyzed after performing potentiodynamic and electrochemical impedance spectroscopic studies. The crystallite size of HNT-PANI composite was calculated and the average size ranged from 30 to 100 nm. HNT-PANI composite electrode exhibited the highest specific capacitance of 282.5 F/g at a current density of 0.5 A/g.

Effect of Halloysite Nanotubes on the Rheological and Phase Separation Behaviors in a Poly(ethylene oxide)/Ionic Liquid Mixture

AbstractA series ternary composites of poly(ethylene oxide)/ionic liquid 30/70 (P30) with uniformly dispersed halloysite nanotubes (HNTs) are investigated in the homogeneous and two‐phase regions. For P30/HNTs composites, a relatively lower percolation threshold about 3 wt% of HNTs loading is observed in the single‐phase region of P30. Beyond the percolation threshold, the steady shear flow exhibits two shear‐thinning regions due to the coupled relaxation of HNTs network and polymer entanglement. In the two‐phase region of P30, the mobility of ionic liquids (ILs) can be impeded accounting for the filler network forming. Not only the phase recovery during cyclic heating–cooling treatment near the phase boundary is accelerated, but also the phase separation kinetics is significantly retarded owing to HNTs dispersed in the PEO‐rich phase impeding the escaping of ILs from PEO phase. The lower storage modulus G′ for P30/HNTs‐4wt% compared to P30/HNTs‐3wt% in a two‐phase region is connected with the competition between the filler contribution and additional elasticity induced by phase separation.