~2H-NMR CHARACTERIZATION OF CLAY DISPERSION AND CONFINEMENT EFFECT ON PROBE MOLECULES IN RUBBER/CLAY NANOCOMPOSITE-GELS

~2H-NMR spectroscopy of the probe molecule,deuterated benzene,was applied to characterize organo-clay dispersion and confinement effect on the local motion of benzene in rubber/clay nanocomposite-gels.The observed ~2H line shapes of benzene in intercalated and exfoliated nanocomposites were obviously different,which can be used to estimate clay-dispersion quality.~2H-NMR line shapes also reflect the different influence of intercalated or exfoliated layered-silicates on local motions of benzene,implying that...

Discussion on“Dispersion characteristics of clayey soils containing waste rubber particles”[J Rock Mech Geotech Eng 15(2023)3050-3058]

We read with great interest the recent article by Erenson(2023)entitled“Dispersion characteristics of clayey soils containing waste rubber particles”.The author has studied the dispersion characteristics of clayey soils containing different percentages of waste rubber particles(WRPs)by performing several tests(viz.consistency limit,linear shrinkage limit,double hydrometer,crumb test and pinhole test)and scanning electron microscopy(SEM)analysis on five clayey(viz.Na-activated bentonite,refined ball clay,Ukrainian kaolin,Avanos kaolin and Afyon clay)samples containing 0%,5%,10%and 15%WRPs.It should be noted that Erenson(2023)has presented some interesting observations,but there are some serious issues that we want to share through this discussion and request the author of the original paper to address them to avoid their persistence in the scientific literature.

Preparation and Characterization of Natural Rubber/Silica Nanocomposites using Rule of Similarity in Latex

Rule of similarity and latex compounding techniques were combined for the first time to prepare natural rubber/nanosilica （NR/SiO2） nanocomposite with core-shell nanosilica-poly （methyl methacrylate） （SiO2-PMMA） particles and PMMA-modified natural rubber matrix （NR-PMMA）. The micro- structure of SiO2 and nanocomposites with different SiO2 contents was characterized by fourier transform infrared spectroscopy （FTIR）; the morphology of nanocomposites was investigated with scanning electron microscopy （SEM）; the tensile strength was characterized by tensile testing machine and the thermal stability of composites was studied by thermal gravimetric analysis. Results showed that PMMA chains have successfully grafted onto the surface of SiO2, and the core-shell SiO2-PMMA nanoparticles and NR-PMMA latex have been perfectly incorporated. SiO2-PMMA nanoparticles are evenly distributed over the NR matrix with an average size in the range of 60-100 nm at the low content （SiO2≤ 3 wt%）, while aggregations are apparently observed when 5 wt% SiO2 is loaded. In addition, NP/SiO2 composities possess a considerable improvement in ageing resistance compared with the pure NR. The tensile strength of composite increases from 6.99 to 12.72 MPa, reaching the highest value at a 0.5 wt% SiO2 loading, and then the figure decreases gradually because of the aggregation of SiO2 nanoparticles. It is anticipated that the reported process is to provide a simple and economic way for preparing NR composites.

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 ...

Dielectric and Microwave Properties of Natural Rubber Based Nanocomposites Containing Graphene

The development of carbon nanotubes based materials has been impeded by both their difficult dispersion in the polymer matrix and their high cost. The discovery of graphene and the subsequent development of graphene-based polymer nanocomposites is an important addition in the area of nanoscience and technology. In this study the influence of graphene nanoparticles (GNP) in concentrations from 2.0 to 10.0 phr on the dielectric (dielectric permittivity, dielectric loss angle tangent) and microwave (reflection coefficient, attenuation coefficient, shielding effectiveness) properties of nanocomposites on the basis of natural rubber has been investigated in the wide frequency range (1 - 12 GHz). The results achieved allow recommending graphene as a filler for natural rubber based composites to afford specific dielectric and microwave properties, especially when their loading with the much more expensive carbon nanotubes is not possible.

Nanocomposite Polymer Hydrogels Reinforced by Carbon Dots and Hectorite Clay

Herein, two nanoparticles with different dimensions, spherical carbon dots (C-dots) and sheetlike hectorite clay, were used as physical crosslinkers to fabricate C-dots-clay-poly(N-isopropylacrylamide)nanocompositehydrogels (coded as C-dots-clay-PNIPAm hydrogels). The mechanical properties, fluorescence features and thermal-responsive properties of the C-dots-clay-PNIPAm hydrogels were evaluated. The experimental results indicate that synergistic effects of C-dots and hectorite clay nanoparticles are able to significantly enhance mechanical properties of the hydrogels. The hydrogels can be stretched up to 1730%with strength as high as 250 kPa when the C-dots concentration is 0.1wt%and the clay concentration is 6wt%. The hydrogels exhibit complete self-healing through autonomic reconstruction of crosslinked network a damaged interface. The hydrogels show favorable thermal-responsive properties with the volume phase transition around 34℃. In addition, the hydrogels are endowed with fluorescence features that are associated with C-dots in the hydrogels. It can be expected that the as-fabricated C-dots-clay-PNIPAm hydrogels are promising for applications in sensors, biomedical carriers and tissue engineering.

Fracture behavior of hybrid epoxy nanocomposites based on multi-walled carbon nanotube and core-shell rubber

The dispersion of nanoparticles plays a key role in enhancing the mechanical performance of polymer nanocomposites.In this work,one hybrid epoxy nanocomposite reinforced by a well dispersed,zinc oxide functionalized,multi-wall carbon nanotube (Zn O-MWCNT) and core-shell rubber (CSR) was prepared,which possesses both high modulus and fracture toughness while maintaining relatively high glass transition temperature (Tg).The improved fracture toughness from 0.82 MPa mfor neat epoxy to 1.46 MPa mfor the ternary epoxy nanocomposites is resulted from a series of synergistic toughening mechanisms,including cavitation of CSR-induced matrix shear banding,along with the fracture of MWCNTs and crack deflection.The implication of the present study for the preparation of high-performance polymer nanocomposites is discussed.

PREPARATION AND PROPERTIES OF CLAY/POLY（N-ISOPROPYLACRYLAMIDE-co-A CRYL AMIDE） NANOCOMPOSITE HYDROGELS

A series of clay/poly（N-isopropylacrylamide-co-acrylamide） nanocomposite hydrogels （S-N-M gels） have been successfully prepared by in situ polymerization. The mechanical properties, swelling behavior of S-N-M gels and the transparency changes during polymerization of S-N-M gels have been systematically investigated. Compared to traditional hydrogels, S-N-M gels show excellent tensile properties and their swelling ratio increases with increasing acrylamide （AAm） content. The results of stress relaxation indicate that the stress loss decreases with increasing AAm content. It was surprisingly found that the transparency during all S-N-M gel synthesis changes abruptly, and the changes become more abrupt with increasing N-isopropylacrylamide content. It was concluded that the fact may be related to the hydrophilicity of copolymers. The weaker the hydrophilicity of copolymer, the more apparent the transparency change during S-N-M gels polymerization. We believe the relationship between hydrophilicity of copolymer and transparency changes will help to design novel nanocomposite hydrogels.

Study on Morphology and Mechanical Properties of High-functional Epoxy Based Clay Nanocomposites

Morphology and mechanical properties of clay/high-functional epoxy nanocomposites are investigated. An intercalated morphology is always observed for clay loadings ≤5 wt %. The glass transition temperature （Tg） of the composites decreases with the clay loading, and the impact strength increases first by 10% at 2 wt% clay loading, and is followed by a dramatic decline, while the flexural strength decreases in all cases.

Structure and Properties of Polyamide 11 Nanocomposites Filled with Fibrous Palygorskite Clay

Various amounts(up to 10 wt%)of palygorskite nanofibers functionalized by 3-aminopropyltriethoxysilane(APTES)coupling agent were used to reinforce polyamide 11 nanocomposites prepared by melt compounding.The covalent bonding of the silane on the palygorskite surface was confirmed by infrared spectroscopy and thermogravimetric analysis.X-ray diffraction revealed the retention of theα-form of polyamide crystals upon the addition of both natural and silane treated palygorskite nanorods.All the investigated nanocomposites showed an improvement of the thermal stability,especially when surface treated palygorskite nanofibers were considered.Tensile tests and dynamic mechanical thermal analyses on the prepared materials evidenced how the incorporation of palygorskite nanofibers significantly increased the elastic and the storage moduli of polyamide,and this enhancement was more evident when natural palygorskite nanorods were used.

STRUCTURING & RHEOLOGY OF MOLTEN POLYMER/CLAY NANOCOMPOSITES

The evolution and the origin of“solid-like state”in molten polymer/clay nanocomposites are studied.Usingpolypropylene/clay hybrid(PPCH)with sufficient maleic anhydride modified PP(PP-MA)as compatibilizer,well exfoliationyet solid-like state was achieved after annealing in molten state.Comprehensive linear viscoelasticity and non-lineartheological behaviors together with WAXD and TEM are studied on PPCH at various dispersion stages focusing on time,temperature and deformation dependencies of the“solid-like”state in molten nanocomposites.Based on these,it is revealedthat the solid-structure is developed gradually along with annealing through the stages of inter-layer expansion by PP-MA,the diffusion and association of exfoliated silicate platelets,the formation of band/chain structure and,finally,a percolatedclay associated network,which is responsible for the melt rigidity or solid-like state.The network will be broken down bymelt frozen/crystallization and weakened at large shear or strong flow and,even more surprisingly,may be disrupted by usingtrace amount of silane coupling agent which may block the edge interaction of platelets.The solid-like structure causescharacteristic non-linear rheological behaviors,e.g.residual stress after step shear,abnormal huge stress overshoots in stepflows and,most remarkably,the negative first normal stress functions in steady shear or step flows.The rheological andstructural arguments challenge the existing models of strengthened entangled polymer network by tethered polymer chainsconnecting clay particles or by chains in confined melts or frictional interaction among tactoids.A scheme of percolatednetworking of associated clay platelets,which may in band form of edge connecting exfoliated platelets,is suggested toexplain previous experimental results.

Influence of clay concentration on the morphology and properties of clay-epoxy nanocomposites prepared by in-situ polymerization under ultrasonication

To investigate the effect of clay concentration on the structures and properties of bisphenol-A epoxy/nanoclay composites, three composites with organoclay concentrations of 2.5wt%, 5wt%, and 7.5wt% of the epoxy resin were prepared by in-situ polymerization under mechanical stirring followed by ultrasonic treatment. The clay aggregates on micro-scale indicate the absence of fully exfoliated nanocomposites. The layer space decreases with the increase of clay concentration, which suggests that the exfoliation would be constrained if more clay is added as the ultrasonic force is exerted. The thermal decomposition temperature remains almost unchanged with the increase of clay concentration. The glass transition temperature of the composites decreases slightly with the increase of clay concentration, whereas the storage modulus increases with the increase of clay concentration.

Effect of functionally-graded interphase on the elasto-plastic behavior of nylon-6/clay nanocomposites;a numerical study

In nanocomposites,the interphase thickness may be comparable to the size of nano-particles,and hence,the effect of interphase layers on the mechanical properties of nanocomposites may be substantial.The interphase thickness to the nano-particle size ratio and properties variability across the interphase thickness are the most important affecting parameters on the overall behavior of nanocomposites.In this study,the effect of properties variability across the interphase thickness on the overall elastic and elastoplastic properties of a polymeric clay nanocomposite(PCN)using a functionally graded(FG)interphase is investigated in detail.The results of the computational homogenization on the mesoscopic level show that Young’s modulus variation of the interphase has a significant effect on the overall elastic response of nanocomposites in a higher clay weight ratio(Wt).Moreover,strength variation through the interphase has a notable effect on the elasto-plastic properties of PCNs.Also,the increase or decrease in stiffness of interphase from clay to matrix and vice versa have a similar effect in the overall behavior of nanocomposites.

Fracture Toughness Studies of Polypropylene- Clay Nanocomposites and Glass Fibre Reinfoerced Polypropylene Composites

In this paper, a comparative study on the fracture toughness of woven glass fibre reinforced polypropylene, chopped glass fibre reinforced polypropylene and nanoclay filled polypropylene composites is presented. Nanoclays (Cloisite 15A) of 1 wt. % to 5 wt. % were filled in polypropylene (PP) matrix and they were subjected to fracture toughness stu-dies. The specimen with 5 wt. % nanoclay showed 1.75 times and 3 times improvement in critical stress intensity factor (KIC) and strain energy release rate (GIC), respectively, over virgin PP. On the other hand, 3 wt. % nanoclay PP composites showed superior crack containment properties. These structural changes of composite specimens were examined using Transmission Electron Microscopy (TEM) and X-ray diffraction (XRD) methods. It showed that exfoli-ated nanocomposite structures were formed up to 3 wt. % nanoclay, whereas, intercalated nanocomposite structures formed above 3 wt. % nanoclay in the PP matrix. Furthermore, the woven fibre reinforced PP composites demonstrated superior crack resistant properties than that of clay filled nanocomposites and chopped fibre PP composites. However, KIC and GIC values for woven fibre composites were lesser than that of chopped fibre composites. Moreover, KIC and GIC values for both nanoclay filled PP composites and woven fibre composites are comparable even though the clay filled PP demonstrated catastrophic failure. Also, the crack propagation rate of PP-nanoclay composites is comparable to that of chopped fibre composites.

Improving the Combined State of Rubber-Clay CompositeInterface by Applying Coupling Agent

The surface modification of clay fines was carried out by using silanecoupling agent. By means of IR spectra etc, a study was made on the combined state ofcoupling agent and clay. A rubber--clay composite material with excellent performancehas been prepared.

Preparation and Properties of a New Type of Poly(butylene-terephthalate)with Layered Silicate Nanocomposites

In this paper, poly(butylene-terephthalate)-layered silicate of clay nanocomposites (NPBT) are reported. Their thermal properties, heat distortion temperature (HDT) and crystallization nucleation are investigated. NPBT samples have apparent viscosity over 0.85, HDT of 30℃ to 50℃ higher than that of poly (butylene-terephthalate) (PBT) for clay load from 1.0% to 10.0% (by mass), and higher capability to accommodate clay than other polymers. The nonisothermal crystallization experiments indicate that the better thermal degradation behavior and crystallization rate of NPBT are 50% higher than PBT, and its injection mould processing temperature is lowered from 110℃ to 55℃. NPBT samples are characterized by several techniques. X-ray shows an original clay interlayer distance enlarged from 1.0 nm to 2.5 nm, while both TBM and AFM indicate an average size from 30nm to lOOnm of exfoliated clay layers, and 3%(by mass) of particle agglomeration being phase separated from PBT matrix, which are factors on some mechanical properties decrease of NPBT. The disappearance of spherulitic morphology in NPBT resulted from layers nucleation is detected. Improving NPBT properties by treating clay with long chain organic reagent and controlling the way to load it is suggested.

The Thermal and Mechanical Properties of Ultra-High Molecular Weight Polyethylene/Montmorillonite (UHMWPE/MMT) Nanocomposites Hybrid Gel Using Pressure-Induced Flow (PIF) Processing

Hybrid organic-inorganic polymer nanocomposites incorporating organically modified montmorillonite (MMT) and ultra-high molecular weight polyethylene (UHMWPE) were examined. UHMWPE/MMT hybrid nanocomposites were prepared using gel and pressure-induced flow(PIF) processing methods at a gel weight concentration of 8% UHMWPE with various organoclay contents (0, 0.4, 0.8, 1.2, and 1.6 parts per hundred parts). The interlayer properties of the nanocomposites were studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The thermal and mechanical interfacial properties of the nanocomposites were investigated through thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and the use of a universal test machine (UTM). TEM indicates that the nanocomposites are formed upon dispersion of MMT in the polymer matrix. From the DSC, TGA, and DMA results, we find that the thermal stability of the UHMWPE nanocomposites increases as the MMT content increases. The nanocomposites show higher tensile strengths than pure UHMWPE gel sheet. These findings indicate that the interfacial and mechanical properties are improved by the addition of MMT and PIF processing.

Incorporation of Clay into Natural Rubber (Hevea) for the Production of Tile Adhesive

Natural rubber latex is the white liquid in the form of the colloidal dispersion of rubber globules suspended in the aqueous liquid. Produced in large quantities in Ivory Coast, the local transformation of natural latex has so far remained insignificant, although some attempts have been made to use it in the manufacture of flexible facade briquettes for rounded walls. Thus, this study aims to incorporate clay as a filler in natural latex for use as an adhesive for tile installation. To do this, different proportions of clay paste were added to the natural latex and the resulting mixtures were used to make the sample and tile adhesive. From the analysis of the results obtained, it appears that the samples with a clay paste density of 0.8 and 1 absorb less water and shows good pull-out strength. The mixtures of 30% and 35% latex and 0.8 and 1 clay paste density respectively have pullout stresses greater than 1 N/mm2. According to NF EN 1348, these adhesives can therefore be used as tile adhesive.

STRUCTURE AND PROPERTIES OF ISOBUTYLENE-ISOPRENE RUBBER/SWOLLEN ORGANOCLAY NANOCOMPOSITES PREPARED BY SHEAR MIXING

A new approach was developed to prepare high-performance isobutylene-isoprene rubber/swollen organoclay nanocomposites by shear mixing.Compared with traditional melt compounding method,better dispersion of nanoclay layers in rubber matrix was verified through transmission electron microscopy（TEM） and X-ray diffraction（XRD）.The nanocomposites also exhibit significantly improved mechanical properties and gas barrier property.As a mechanism,the molecules of organic swelling agent play a vital role in accelerating the diffusion and intercalation of the matrix molecules.