Hybrid Nanoparticle–Polymer Brush Composites for Detection of Low‐Level Radiostrontium in Water

Combining extraction and scintillation properties within the same material is a relatively new approach in development of sensors for detection of radioactive elements. Structural organization of such materials at a nanoscale typically offers higher efficiency of detection and shorter response time. In this contribution, several new protocols are discussed for fabrication of stable extractive scintillating systems based on commercial Superlig 620 (SL) material with high affinity to radiostrontium. Application of hybrid organic–inorganic beads with SL particles used as core and halloysite clay nanotubes (HNT) modified with a polyvinyltoluene (PVT) brush as a permeable shell combines high‐performance extracting properties of the SL material with efficient light emission properties of the polymer scintillator. The developed SL–HNT–PVT hybrid extractive scintillating material allows real‐time detection of low‐level concentrations of radiostrontium in water. Moreover, the suggested approach is not limited to detection of Sr but can find broader application in development of chemical, biological, or radioluminescent sensors and multifunctional materials.     

Influence of shape and surface modification of nanoparticle on the rheological and dynamic‐mechanical properties of polyamide 6 nanocomposites

Nanocomposites of polyamide 6 (PA6) with different concentrations of silane‐treated, organic‐treated, and nontreated nanoparticles of halloysite (HNT) and montmorillonite (MMT) had their microstructure and melt and solid state rheological behavior analyzed. The microstructure analysis was done using transmission electron microscopy (TEM) and wide angle X‐ray diffraction (WAXD); the effectiveness of the silanization was studied by thermogravimetric analysis (TGA) and Fourier transform infrared. It was found that exfoliation occurred in the organic‐treated MMT, but not in the silane‐treated MMT and that silanization was small in the HNT nanoparticles (due to its low amount of surface hydroxyls groups). Steady state shear, small amplitude oscillatory, and transient tests also indicated that: (i) only the nanocomposites with organic‐treated MMT, at concentrations above the theoretical percolation threshold developed a percolated network; (ii) the silane treatment increased the shear elastic modulus (G) of the PA6/HNT nanocomposites in the solid state, but not of the PA6/MMT; (iii) the organic‐treated MMT formed composites with the highest G, as expected. Thus, it was concluded that the HNT nanoparticles had a high potential as nanofiller for PA6, but further research on more efficient compatibilizers for HNT is still needed. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers.     

Thermal Insulation Characteristics of Polybenzoxazine Aerogels

Polybenzoxazine (PBO) aerogels with low densities and low thermal conductivities are prepared from Bisphenol A (BPA) benzoxazine monomers by ring‐opened polymerisation using HCl as a catalyser at 10 °C. The obtained PBO aerogels have cross‐linked and 3D network structures with the densities ranging from 0.084 to 0.526 g cm^?3. The thermal conductivities under different pressures (3–10⁵ Pa, air) and different atmospheres (N₂, Ar, and CO₂, 10⁵ Pa) are investigated. The thermal conductivities are in the range of 0.0335–0.0652 W m K^?1 under ambient pressure and 0.0098–0.0571 W m K^?1 at 3 Pa. The thermal transfer mechanism under different gas pressures is analyzed with increasing pressure. Under different atmospheres, the thermal conductivities decrease as the molecular weight of the gas increases. Compared with the traditional organic foam insulating materials of phenolic foam, polyurethane and polystyrene, which have similar apparent densities, PBO aerogels exhibit lower thermal conductivity of 0.0335 W m K^?1 than that of traditional organic foam at room temperature.     

Biocompatible regenerated cellulose/halloysite nanocomposite fibers

Regenerated cellulose (RC) bio-nanocomposite fibers reinforced with halloysite nanotubes (HNT) were fabricated through wet spinning technique via ionic liquid as a green solvent. Mechanical properties, water uptake, thermal stability, and cytocompatibility of the obtained fibers were examined. FTIR spectra indicated the uniform dispersion of HNT in the cellulose network. XRD analysis, together with FE-SEM images indicated that HNT was dispersed homogenously in the polymer. Moreover, mechanical and thermal stabilities of the nanocomposite fibers were notably increased through the addition of HNT. Eventually, human skin fibroblasts proliferation on nanocomposite fibers demonstrated good cyto-compatibility. These findings highlight the potential of HNT nanocomposite fibers for biological and biomedical applications.     

Fabrication and characterization of mesoporous carbon nanosheets using halloysite nanotubes and polypyrrole via a template‐like method

A novel synthesis route for mesoporous carbon (MC) nanosheets were developed using halloysite nanotubes (HNTs), a type of natural clay that is structurally and chemically similar to mineral kaolinite, as inorganic matrix and using polypyrrole (PPy) as carbon precursor by a template‐like method. First, PPy/HNT hybrids were prepared by in situ oxidative polymerization. Carbon (C)/HNT hybrids were further obtained by pyrolysis of the PPy/HNT hybrids. MC was obtained after the removal of inorganic template by hydrochloric acid/hydrofluoric acid mixture at the end. Both the C/HNT and the MC were characterized by Fourier transform infrared spectroscopy analysis, X‐ray diffraction, Raman spectra measurement, and high‐resolution transmission electron microscopy. The MC was also characterized with specific surface area (BET). The results showed that the MC obtained was almost amorphous carbon. The increase in the ratio of [HNTs template]/[pyrrole monomer] led to an increase in the BET‐specific surface area. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Preparation of viscoelastic gel‐like halloysite hybrids and their application in halloysite/polystyrene composites

Self‐reinforcement gel‐like halloysite nanotube (g ‐HNT ) hybrids with various viscoelastic behaviors were fabricated by firstly treating with various concentrations of sodium hydroxide (NaOH ) solution and then grafting tertiary amine and ion‐exchange reacting with sulfonate anions. The morphology, composition, thermal stability and rheological behavior of the g ‐HNT hybrids were systematically characterized and analyzed using various methods. It is found that the viscoelasticity of g ‐HNT hybrids can be easily regulated by using different NaOH solution‐treated HNTs as inorganic core and temperatures. In addition, the g ‐HNT hybrids treated with medium concentration of NaOH (0.06 mol L^?1) have the lowest viscosity and highest level of dispersion compared with those treated with other concentrations of NaOH solution. Due to the amphiphilic nature of g ‐HNT hybrids and their lower viscosity than HNT powder, as novel hybrid fillers, they were utilized to prepare polystyrene composites by direct melt blending for achieving simultaneous reinforcement and plasticization effects. Besides the above mentioned advantages, the thermal conductivity of polystyrene composites is also surprisingly improved by reducing the interfacial mismatch between the filler and polymer matrix. The solvent‐free and self‐reinforcement hybrids provide a convenient and green path for fabricating high‐performance polymer composites. © 2017 Society of Chemical Industry     

Characterization of hyperporous polyurethane-based gels by non-intrusive mercury porosimetry

Evaporative drying of polyurethane-based gels produces xerogels. Supercritical drying after replacement of interstitial liquid by supercritical CO₂ produces aerogels. SEM micrographs show that both materials are made up of small size particles gathered up in filament-shaped, strongly cross-linked aggregates. Density measurements show that they both have a large pore volume.When submitted to mercury porosimetry, the behavior of these materials is similar to that of inorganic aerogels, as previously observed. Mercury does not penetrate the pore network, but the whole material is densified. The usual Washburn equation cannot be used to analyze the mercury porosimetry. A well-suited equation based on a buckling model of filament-shaped aggregates has been developed in order to determine the pore volume distribution of mineral dried gels. This equation is also valid for analyzing the texture of organic hyperporous materials like polyurethane dried nanoporous gel.     

Halloysite nanotubes immobilized by chitosan/tannic acid complex as a green flame retardant for bamboo fiber/poly(lactic acid) composites

In order to develop an environmentally benign flame retardant for bamboo/PLA composites (BPC), chitosan (CS) and tannic acid (TA) were used as cationic and anionic polyelectrolyte respectively to stabilize halloysite nanotubes (HNT) on the surface of bamboo fiber (BF) and poly(lactic acid) (PLA). Mechanical performance tests showed that the flexural properties of BPC were moderately enhanced with the addition of HNT, while the incorporation of CS/TA complex (FR) exhibited a slight increase. The results of thermogravimetric analysis demonstrated that CS/TA complex and HNT improved the thermal stability of the BPC synergistically, which increased the char residue. Limiting oxygen index and cone calorimetry tests were used to study the flammability of BPC and the results showed that the addition of CS/TA complex and HNT had a synergistic effect on the flame retardant performance of BPC materials. The macroscopic and microscopic morphological studies confirmed the formation of HNT layer in the matrix of BPC/5FR@5HNT samples, which facilitated more stabile char residue with the best flame retardant performance.     

Synthesis and Characterization of Mesoporous Hybrid Silica-Polyacrylamide Aerogels and Xerogels

We report the synthesis of highly porous hybrid silica-polyacrylamide aerogels where the inorganic network was obtained through the hydrolysis and poly-condensation of tetramethoxysilane via a two-step sol–gel process while the polyacrylamide polymer was made by photo-copolymerization of two organic monomers, the acrylamide and the bis-acrylamide. These aerogels were obtained after a carbon dioxide supercritical drying while the corresponding xerogels were dried by simple evaporation. These materials, as well as pure silica and polyacrylamide aerogels and xerogels, were characterized by FTIR spectroscopy, solid-state ²⁹Si and ¹³C NMR spectroscopy, Thermogravimetric Analysis, a nitrogen adsorption-desorption technique, and Scanning Electron Microscopy. The FTIR and NMR spectra and the TGA/DTA analyses confirm the coexistence of highly branched silica and polyacrylamide networks reflecting the hybrid nature of the materials obtained. Nitrogen adsorption measurements reveal high specific surface areas and pore size distributions disclosing the mesoporous character of these hybrid materials. Hybrid silica-polyacrylamide aerogels having a specific surface area equal to 572 m²/g and a pore volume 1.92 cm³/g were successfully prepared for the first time in this study. The high porosity of these aerogels is due to a better resistance of the silica network to capillary forces during the supercritical drying when silica coexists with a polyacrylamide network.     

Comparison of natural halloysite with synthetic carbon nanotubes in poly(lactic acid) based composites

The objective of this study is to compare the mechanical properties, structure and degradability of the nanocomposites prepared with tubular nanofillers, halloysite (HNT) and carbon nanotube (CNT) in poly(lactic acid) (PLA), and thermoplastic polyurethane (TPU) toughened PLA (T‐PLA) matrices. In the PLA matrix, CNT increased, whereas HNT decreased the tensile strength with increasing filler content. Also, the elongation at break and impact strength decreased with increasing CNT content, but these properties were relatively unchanged with increasing HNT content. However, when (TPU) was used as an impact modifier‐compatibilizer, addition of HNT further increased the impact strength and the elongation at break of the matrix, since short and straight HNT fibers were pulled out from the extensible, toughened matrix. The long and curvy CNT fillers always caused brittle fracture and affected the impact strength and elongation at break in a negative manner as the CNT content was increased. Both types of fillers did not significantly influence the degradation of PLA or toughened PLA matrices. POLYM. COMPOS., 38:2337–2346, 2017. © 2015 Society of Plastics Engineers     

Capped inhibitor-loaded halloysite nanoclay-based self-healing silica coatings for corrosion protection of mild steel

The effect of polymeric nanocapsule capping in benzotriazole encapsulated into halloysite nanoclay (HNTs) dispersed into hybrid silica coatings was investigated for corrosion protection of mild steel. Optimization of the amount of inhibitor-loaded halloysite nanotubes with and without capping in the coating sol was carried out. The prepared formulations were dip-coated on mild steel substrates using dip-coater and then cured at 130 °C for 1 h. Surface morphology and elemental analysis of the nanoclay were studied using scanning electron microscopy and energy dispersive X-ray spectroscopy. X-ray diffraction and Fourier Transform Infrared spectroscopy analyses were carried out to confirm the encapsulation and capping of the halloysite nanoclay. The anti-corrosion and autonomic-healing properties of bare and coated substrates in 3.5 wt% NaCl solution were studied using electrochemical impedance spectroscopy, potentiodynamic polarization measurements and scanning vibrating electrode technique for varying exposure times. The coatings generated from the capped inhibitor-loaded HNTs dispersed sol-gel matrix was seen to provide higher corrosion resistance when compared to uncapped HNT based silica coatings. Electrochemical studies carried out for capped inhibitor-loaded HNT based coatings have shown an increase in charge transfer resistance to 10⁸ Ω cm² from 10⁶ Ω cm² of uncapped inhibitor-loaded HNT based coatings.     

Elaboration and properties of novel biobased nanocomposites with halloysite nanotubes and thermoplastic polyurethane from dimerized fatty acids

Nanocomposites of biobased thermoplastic polyurethane (TPU) from dimer fatty acids and halloysite nanotubes (HNT) were elaborated by different melt processing routes such as direct mixing (1 step process) and masterbatch/dilution (2 steps process), at different temperatures (150 and 180 °C). Rheological and transmission electron microscopy (TEM) analyses indicated that the HNT distribution and dispersion were dependent on the processing conditions: the 2 steps process produced well dispersed nanocomposites and the masterbatch dilution at 180 °C improved the HNT distribution through the TPU. Consequently, a high reinforcement was achieved, with a 40% increase in the elastic modulus and 8 °C increase in the relaxation temperature related to the glass transition of the TPU soft segments. Furthermore, a percolated network was attained, even if a large extent of HNT breaking was observed during processing, suggesting that a synergistic effect between the HNT particles and the TPU's hard segments in the molten state occurred. Thus, HNT nanotubes can be seen as highly reinforcing nanofillers when good dispersion and distribution are achieved through the polymeric matrix.     

Hydrophobic,Pore‐Tunable Polyimide/Polyvinylidene Fluoride Composite Aerogels for Effective Airborne Particle Filtration

Polyimide (PI) aerogels have great potential as filter materials, owing to their unique porous structure and excellent thermodynamic properties. In this work, polyvinylidene fluoride (PVDF) is introduced into the 3D network structure of crosslinked PI by phase separation to prepare PI/PVDF hybrid aerogels. By adding different amounts of PVDF, effective control of the aerogel porous structure is achieved, as a result, the air permeability of the hybrid aerogel is significantly improved while still achieving a filtration efficiency of airborne particulates of more than 99.8%. PVDF is aggregated and dispersed on the surface or inside of the aerogel in the form of nanoparticles, which effectively increases the hydrophobicity of the material. The contact angle of the prepared PI hybrid aerogel is ≈150°, and the water absorption is as low as 2.2%, which enables the aerogel to maintain structural stability in humid environments. In addition, the aerogel exhibits good adsorption effects on organic solvents.     

Aerogels—Nanoporous materials part I: Sol-gel process and drying of gels

Aerogels are highly porous nanostructured materials made in a sol-gel process, generally followed by supercritical drying in an autoclave. Today considerable activities are also devoted to subcritical drying under ambient conditions. Aerogels have been made of inorganic substances such as SiO₂, Al₂O₃, TiO₂ etc. or organic components (resorcinol and melamine formaldehyde) in transparent, translucent and opaque form. Even electrically conductive carbon aerogels are available today. An important step with respect to mass application is the production of granular SiO₂-aerogels with water glass as a precursor. Also of practical importance is the hot-pressing of aerogel sheets from granular or powdered fills.In this paper we shall describe the formation of the organic and inorganic gels and the various procedures to extract the pore fluid without or with little shrinkage. A subsequent paper will be devoted to the characterization and the application of aerogels.     

Effect of halloysite nanotubes on mechanical properties and flammability of soy protein based green composites

To address the growing emphasis on the use and development of sustainable materials, bio‐based polymers and fibers are processed to prepare entirely bio‐based fiber‐reinforced ‘green’ composites. To enable these new materials to perform in lightweight vehicle and infrastructural applications, they must be characterized both structurally and in terms of their various performance characteristics. The results of preparation and characterization of bio‐based composites comprising jute fabric and soy protein concentrate (SPC) modified with glycerol and/or halloysite nanotubes (HNT) are reported herein as a first look at the flammability of these bio‐based nanocomposites. The results reveal that SPC has lower flammability (heat release capacity) than petrochemical‐based resins, such as epoxies and vinyl esters. In addition, incorporating 5% mass fraction of HNT is found to reduce the composite flammability, while having no negative impact on the mechanical properties. Copyright © 2012 John Wiley & Sons, Ltd.     

Emerging Synthetic Methods and Applications of MOF-Based Gels in Supercapacitors,Water Treatment,Catalysis, Adsorption,and Energy Storage

Metal–organic frameworks (MOFs), which are synthesized through the self-assembly of organic ligands and inorganic metals, have drawn considerable research interest owing to their unique properties and attractive structures. Many studies on various MOF derivatives, such as MOFs and cellulose aerogels, hydrogel composite materials, and bimetallic-centered MOF materials, have provided the potential for wide application of MOFs. However, MOFs mostly exist in the form of powder particles, which are difficult to form. In addition, MOFs have problems with structural instability. MOF-based gels can overcome this problem. MOF-based gels also have significant advantages in secondary processing. In this review, synthetic methods for MOF-based gels, particularly the synergistic effect with other materials, are introduced. The applications of MOF-based hydrogels and aerogels in supercapacitors, water treatment, catalysis, adsorption, and energy storage are also discussed.     

Halloysite nanotube reinforced polylactic acid composite

Polylactic acid (PLA) has a long history in medical applications. Reinforced PLA has the potential to be used in the medical applications that require high mechanical strength such as coronary stents and bone fixation devices. Halloysite nanotube (HNT) has received considerable attention recently due to its tubular structure, high aspect ratio, high mechanical strength, thermal stability, biocompatibility and sustained drug releasing properties. Halloysite has been investigated in compounding with many polymers. However, the research in compounding halloysite with biodegradable materials for use in biological applications is sparse. In this study various weight fractions of HNT was compounded with the biodegradable polymer PLA using a melt compounding method. Tensile test, Fourier infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), contact angle test, scanning electron microscopy (SEM), void content and thermogravimetric analysis (TGA) were carried out to study the PLA/HNT composite. Tensile test results indicated that Young's modulus and stiffness of PLA were enhanced with the addition of HNT; FTIR spectra showed the interaction between the PLA and HNT; whereas contact angle measurements indicated that the wettability of the PLA/HNT composite was not affected by the addition of HNT. However, the thermal stability of PLA was adversely effected by the addition of HNT which may be related to the presence of voids between the polymer and matrix. Nevertheless, the reinforced PLA/HNT composite, which maintains the surface characteristics, may prove beneficial for use in biological applications. POLYM. COMPOS., 38:2166–2173, 2017. © 2015 Society of Plastics Engineers     

Flexible polyurethane foams reinforced with organic and inorganic nanofillers

The effect of three different types of cellulose nanofillers on the morphology, mechanical, and thermal properties of flexible polyurethane foam was studied. Cellulose nanocrystals (CNC), cellulose nanofibrils (CNF), and cellulose filaments (CelFil) were used as fillers at 0.1–0.8 wt% loading levels. The comparison of the results showed that smaller loading levels resulted in foams with better performance in almost all cases. In the next step, the properties of foams containing CNC, CNF, or CelFil at 0.025%–0.1% loading levels were compared with those made with inorganic nanofillers including nanosilica (nSi), reduced graphene oxide, and halloysite nanotubes (HNT). Among all the properties evaluated, the tensile modulus of the foams was improved up to 40% by adding HNT at 0.05 wt% loading level whereas the addition of CNF resulted in a 44% increase in the compressive modulus of the foams at 0.1 wt% loading level.     

Fabrication and biological assessment of halloysite-doped micro/nano structures on titanium surface

Titanium (Ti) is widely used as a biomaterial for dental implants, but its insufficient angiogenic and osteogenic properties prolong the restoration period. In this study, halloysite nanotubes (HNTs) were embedded on the surface of Ti via micro arc oxidation (MAO) treatment to enhance its early osseointegration. The surface physiochemical properties were examined, and the results confirmed that HNTs were successfully incorporated into the MAO coating. It was also discovered that the surface wettability and negative charge of the corresponding samples increased. In cytocompatibility tests involving human umbilical vein endothelial cells (HUVECs) and MC3T3-E1 cells, the HNT group exhibited no cytotoxicity compared with the MAO group and the best performance for cell adhesion and spreading among the three groups (Ti, MAO and HNT). Regarding angiogenesis, the HNT group outperformed the Ti and MAO groups in cell migration, tube formation, and angiogenic gene expression of HUVECs. Furthermore, with regard to osteogenesis, the HNT group exhibited the highest levels of alkaline phosphatase activity, collagen secretion, mineralized calcium nodules, and osteogenic gene expression of MC3T3-E1 cells among the three groups with significant differences. These findings indicated that the HNT specimens could significantly promote angiogenesis as well as osteogenesis at both the cellular and molecular levels.     

Influence of Halloysite Nanotube on Properties of Tire Tread Compounds Filled with Silica and Carbon Black Hybrid Filler

Properties of solution styrene butadiene rubber (SSBR), based on passenger car tire tread formulation, filled with silica/carbon black/halloysite nanotube (SiO₂/CB/HNT) hybrid filler were investigated. Effect of HNT was studied by partially replacing CB in the reference compound with 0–16 phr of HNT. With increasing HNT content, mechanical properties such as modulus, hardness, tensile strength, tear strength and abrasion resistance are impaired, due to the combination of low specific surface area of HNT (compared with CB), poor rubber-HNT interaction and poor HNT dispersion. However, the partial replacement of CB with HNT leads to the improvement of wet grip and rolling resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46987.