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.

TOUGHENING OF ETHYLENE-PROPYLENE RANDOM COPOLYMER/CLAY NANOCOMPOSITES:COMPARISON OF DIFFERENT COMPATIBILIZERS

Ethylene/propylene-random-copolymer （PPR）/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers, including an ethylene-octene copolymer grafted maleic anhydride （POE-g-MA） and three maleic-anhydride-grafted polypropylenes （PP-g-MA） with different melt flow indexes （MFI）, were used to improve the dispersion of organic clay in matrix. On the other hand, the effects of organic montmorillonite （OMMT） content on the nanocomposite structure in terms of clay dispersion in PPR matrix, thermal behavior and tensile properties were also studied. The X-ray diffraction （XRD） and transmission electron microscopy （TEM） results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites. Moreover, a PP-g-MA compatibilizer （compatibilizer B） having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers. With the introduction of compatibilizer D （POE-g-MA）, most of the clays are dispersed into the POE phase, and the shape of the dispersed OMMT appears elliptic, which differs from the strip of PP-g-MA. Compared with virgin PPR, the Young＇s modulus of the nanocomposite evidently increases when a compatibilizer C （PP-g-MA） with medium MFI is used. For the nanocomposites with compatibilizer B and C, their crystallinities （Xc） increase as compared with that of the virgin PPR. Furthermore, the increase of OMMT loadings presents little effect on the melt temperature （Tc） of the PPR/OMMT nanocomposites, and slight effect on their crystallization temperature （Tc）. Only compatibilizer B can lead to a marked increases in crystallinity and Tc of the nanocomposite when the OMMT content is 2 wt%.

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.

Some basic aspects of polymer nanocomposites: A critical review

Polymer nanocomposites have been investigated for about three decades. To get deep insights into the modifying effects of various nanofillers on mechanical and physical properties of polymer nanocomposites, the three basic aspects of processing, characterization and properties are critically reviewed in this paper. Nanofillers can be classified into three major types of two-dimensional (2D) layered, one-dimensional (1D) fibrous and zerodimensional (0D) spherical ones and this review thus discusses in detail the processing, characterization and properties of the three types of polymer nanocomposites. It starts with an introduction of various nanoscale fillers such as two-dimensional (2D) nano-clay, graphene and MXene, one dimensional (1D) carbon nanofibers and nanotubes, zero dimensional (0D) silica nanoparticles and ZnO quantum dots as well as nanofiller-polymer interfaces. The processing of these polymer nanocomposites using different methods and the characterization of nanofillers and polymer nanocomposites using various techniques are described. Finally, the mechanical and physical properties of these polymer nanocomposites are discussed by considering the effects of nanofiller type, dispersion and contents;also, interface properties show significant effects on the mechanical properties of polymer nanocomposites and are discussed in some details.

Recent Advances in Fabrication and Characterization of Graphene-Polymer Nanocomposites

Graphene has attracted considerable interest over recent years due to its intrinsic mechanical, thermal and electrical properties. Incorporation of small quantity of graphene fillers into polymer can create novel nanocomposites with im- proved structural and functional properties. This review introduced the recent progress in fabrication, properties and potential applications of graphene-polymer composites. Recent research clearly confirmed that graphene-polymer na-nocomposites are promising materials with applications ranging from transportation, biomedical systems, sensors, elec-trodes for solar cells and electromagnetic interference. In addition to graphene-polymer nanocomposites, this article also introduced the synergistic effects of hybrid graphene-carbon nanotubes (CNTs) on the properties of composites. Finally, some technical problems associated with the development of these nanocomposites are discussed.

Layered Foam/Film Polymer Nanocomposites with Highly Efficient EMI Shielding Properties and Ultralow Reflection

Lightweight,high-efficiency and low reflection electromagnetic interference(EMI)shielding polymer composites are greatly desired for addressing the challenge of ever-increasing electromagnetic pollution.Lightweight layered foam/film PVDF nanocomposites with efficient EMI shielding effectiveness and ultralow reflection power were fabricated by physical foaming.The unique layered foam/film structure was composed of PVDF/SiCnw/MXene(Ti_(3)C_(2)Tx)composite foam as absorption layer and highly conductive PVDF/MWCNT/GnPs composite film as a reflection layer.The foam layer with numerous heterogeneous interfaces developed between the SiC nanowires(SiCnw)and 2D MXene nanosheets imparted superior EM wave attenuation capability.Furthermore,the microcellular structure effectively tuned the impedance matching and prolonged the wave propagating path by internal scattering and multiple reflections.Meanwhile,the highly conductive PVDF/MWCNT/GnPs composite(~220 S m^(−1))exhibited superior reflectivity(R)of 0.95.The tailored structure in the layered foam/film PVDF nanocomposite exhibited an EMI SE of 32.6 dB and a low reflection bandwidth of 4 GHz(R<0.1)over the Kuband(12.4-18.0 GHz)at a thickness of 1.95 mm.A peak SER of 3.1×10^(-4) dB was obtained which corresponds to only 0.0022% reflection efficiency.In consequence,this study introduces a feasible approach to develop lightweight,high-efficiency EMI shielding materials with ultralow reflection for emerging applications.

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.

Vapor Phase Polymerization Deposition Conducting Polymer Nanocomposites on Porous Dielectric Surface as High Performance Electrode Materials

We report chemical vapor phase polymerization(VPP) deposition of poly(3,4-ethylenedioxythiophene)(PEDOT) and PEDOT/graphene on porous dielectric tantalum pentoxide(Ta_2O_5) surface as cathode films for solid tantalum electrolyte capacitors. The modified oxidant/oxidant-graphene films were first deposited on Ta_2O_5 by dip-coating, and VPP process was subsequently utilized to transfer oxidant/oxidant-graphene into PEDOT/PEDOT-graphene films. The SEM images showed PEDOT/PEDOT-graphene films was successfully constructed on porous Ta_2O_5 surface through VPP deposition, and a solid tantalum electrolyte capacitor with conducting polymer-graphene nano-composites as cathode films was constructed. The high conductivity nature of PEDOT-graphene leads to resistance decrease of cathode films and lower contact resistance between PEDOT/graphene and carbon paste. This nano-composite cathode films based capacitor showed ultralow equivalent series resistance(ESR) ca. 12 m? and exhibited excellent capacitance-frequency performance, which can keep 82% of initial capacitance at 500 KHz. The investigation on leakage current revealed that the device encapsulation process has no influence on capacitor leakage current, indicating the excellent mechanical strength of PEDOT/PEDOT-gaphene films. This high conductivity and mechanical strength of graphene-based polymer films shows promising future for electrode materials such as capacitors, organic solar cells and electrochemical energy storage devices.

Atomic insights into synergistic effect of pillared graphene by carbon nanotube on the mechanical properties of polymer nanocomposites

Molecular dynamics simulations have been performed to explore the underlying synergistic mechanism of pillared graphene or non-covalent connected graphene and carbon nanotubes(CNTs) on the mechanical properties of polyethylene(PE) nanocomposites. By constructing the pillared graphene model and CNTs/graphene model, the effect of the structure, arrangement and dispersion of hybrid fillers on the tensile mechanical properties of PE nanocomposites was studied. The results show that the pillared graphene/PE nanocomposites exhibit higher Young’s modulus, tensile strength and elongation at break than non-covalent connected CNTs/graphene/PE nanocomposites. The pull-out simulations show that pillared graphene by CNTs has both large interfacial load and long displacement due to the mixed modes of shear separation and normal separation. Additionally, pillared graphene can not only inhibit agglomeration but also form a compact effective thickness(stiff layer), consistent with the adsorption behavior and improved interfacial energy between pillared graphene and PE matrix.

A comparative study of polymer nanocomposites containing multi-walled carbon nanotubes and graphene nanoplatelets

Featuring exceptional mechanical and functional performance, MWCNTs and graphene(nano)platelets(GNPs or Gn Ps;each platelet below 10 nm in thickness) have been increasingly used for the development of polymer nanocomposites. Since MWCNTs are now cost-effective at US$30 per kg for industrial applications, this work starts by briefly reviewing the disentanglement and surface modification of MWCNTs as well as the properties of the resulting polymer nanocomposites. GNPs can be made through the thermal treatment of graphite intercalation compounds followed by ultrasonication;GNPs would have lower cost yet higher electrical conductivity over 1,400 S cmthan MWCNTs. Through proper surface modification and compounding techniques, both types of fillers can reinforce or toughen polymers and simultaneously add anti-static performance. A high ratio of MWCNTs to GNPs would increase the synergy for polymers. Green, solvent-free systhesis methods are desired for polymer nanocomposites. Perspectives on the limitations, current challenges and future prospects are provided.

The roles of polymer-graphene interface and contact resistance among nanosheets in the effective conductivity of nanocomposites

The effective conductivity of graphene-based nanocomposites is suggested by the characteristics of polymer-filler interfacial areas as well as the contact resistance between the neighboring nanosheets.The interfacial properties are expressed by the effective levels of the inverse aspect ratio and the filler volume fraction.Moreover,the resistances of components in the contact regions are used to define the contact resistance,which inversely affects the effective conductivity.The obtained model is utilized to predict the effective conductivity for some examples.The discrepancy of the effective conductivity at various ranks of all factors is clarified.The interfacial conductivity directly controls the effective conductivity,while the filler conductivity plays a dissimilar role in the effective conductivity,due to the incomplete interfacial adhesion.A high operative conductivity is also achieved by small contact distances and high interfacial properties.Additionally,big contact diameters and little tunnel resistivity decrease the contact resistance,thus enhancing the effective conductivity.

Correlating the Interfacial Polar-Phase Structure to the Local Chemistry in Ferroelectric Polymer Nanocomposites by Combined Scanning Probe Microscopy

Ferroelectric polymer nanocomposites possess exceptional electric properties with respect to the two otherwise uniform phases,which is commonly attributed to the critical role of the matrix-particle interfacial region.However,the structure-property correlation of the interface remains unestablished,and thus,the design of ferroelectric polymer nanocompos-ite has largely relied on the trial-and-error method.Here,a strategy that combines multi-mode scanning probe microscopy-based electrical charac-terization and nano-infrared spectroscopy is developed to unveil the local structure-property correlation of the interface in ferroelectric polymer nano-composites.The results show that the type of surface modifiers decorated on the nanoparticles can significantly influence the local polar-phase content and the piezoelectric effect of the polymer matrix surrounding the nano-particles.The strongly coupled polar-phase content and piezoelectric effect measured directly in the interfacial region as well as the computed bonding energy suggest that the property enhancement originates from the formation of hydrogen bond between the surface modifiers and the ferroelectric polymer.It is also directly detected that the local domain size of the ferroelectric polymer can impact the energy level and distribution of charge traps in the interfacial region and eventually influence the local dielectric strength.

Preparation and Characterization of Maltose-Pendant Polymer/Mica Nanocomposites and Their Application to Oxygen Gas Barrier Films

Maltose-pendant polymer/mica nanocomposites were prepared by a solution intercalation method. For organic composite part, 1) maltose-pendant polymer (homopolymer) and 2) the copolymer of maltose-pendant monomer and a small amount of N,N-Dimethylamino propylacrylamide, methyl chloride quartenary were used. The morphological studies (XRD and FE-SEM) revealed that the hybrid of maltose-pendant polymer was a conventional phase separated composite. On the other hand, the hybrid using the copolymer exhibited exfoliated structure. Both the conventional composite of maltose-pendant polymer and the nanocomposite of copolymer were applied to a coating material for oxygen gas barrier layer on a nylon-6 film, and oxygen transmission rates of the films were evaluated. Maltose-pendant polymer had a good oxygen barrier property under dry condition, and the barrier property under wet condition was improved by the hybridization with mica. In contrast, the barrier property of copolymer was slightly inferior to that of maltosependant polymer. However, under dry condition, it can be seen that the nanocomposite of copolymer improves the barrier property more effectively than the case of conventional composite of maltose-pendant polymer.

Probing Nanoscale Morphology of PS/PMMA/CdS &PS/PVC/CdS Polymeric Nanocomposites through Small Angle X-Ray Scattering Analysis

Polymeric nanocomposites of PS/PMMA/CdS and PS/PVC/CdS samples have been synthesized through dispersion solution casting technique. The nanoparrticles of CdS were prepared by simple chemical method using CdCl2 and H2S gas produced from thiourea. The nanoscale morphology of the prepared polymeric nanocomposite samples is probed through small angle X-ray scattering (SAXS). The SAXS study reveals that CdS nanoparticles take place at voids position in the respective plymer blend matrix and exhibit their nano nature with very little tendency to agglomerates.

Experimental Study on Polymer Nanocomposites Based Strain Sensors for Structural Health Monitoring

The aim is to develop a mechanically flexible polymer nanocomposite film-based strain sensors that could act towards sustainable structural health monitoring for civil structures. The developed polymer nanocomposite film combinations will be monitored for their structural, electrical and mechanical behaviors and the optimized formulations will be tried for strain sensing applications. The films were cast by using PVA as the base polymer and copper doped silver nitrate as the nanofiller along with the use of glycine as fuel which is a combination of silver and copper nitrate. After preparing the films, they were tested for conductivity under tensile loading using a digital multi meter connected to a UTM. The samples were subjected to XRD, FTIR and SEM for further analysis. The results of the experiments shown I-V characteristics of PVA-CuAgO composites from 5% to 25% CuAgO have been increased tremendously with the incorporation of filler material. For 100 V, the maximum current value obtained for plain PVA is only 7.7E-8 A, whereas CuAgO particles shown 0.0025 A at 5% reinforcements and further increased nearly to 0.025 A for 25% of CuAgO particles into the PVA matrix.

Modeling and Simulation of Graphene Based Polymer Nanocomposites: Advances in the Last Decade

Modeling and simulation allow methodical variation of material properties beyond the capacity of experimental methods. The polymers are one of the most commonly used matrices of choice for composites and have found applications in numerous fields. The stiff and fragile structure of monolithic polymers leads to the innate cracks to cause fracture and therefore the engineering applications of monolithic polymers, requiring robust damage tolerance and high fracture toughness, are not ubiquitous. In addition, when “many-parts” cling together to form polymers, a labyrinth of molecules results, which does not offer to electrons and phonons a smooth and continuous passageway. Therefore, the monolithic polymers are bad conductors of heat and electricity. However, it is well established that when polymers are embedded with suitable entities especially nano-fillers, such as metallic oxides, clays, carbon nanotubes, and other carbonaceous materials, their performance is propitiously improved. Among various additives, graphene has recently been employed as nano-filler to enhance mechanical, thermal, electrical, and functional properties of polymers. In this review, advances in the modeling and simulation of grapheme based polymer nanocomposites will be discussed in terms of graphene structure, topographical features, interfacial interactions, dispersion state, aspect ratio, weight fraction, and trade-off between variables and overall performance.

Synthesis of Polymer Nanocomposites for Selective Laser Sintering （SLS）

This paper presents initial development of polymer application. PNC materials containing a polyamide （PA） and nano to improve the mechanical properties. Commercial polyamide 6 nanocomposites （PNC） material for rapid manufacturing （RM） particles （5 wt%） were produced by solution blending with the aim （PA6） was dissolved in formic acid （HCO2H） together with two different types of nano particle materials： yttrium stabilised zirconia （YSZ） and Hectorite clay （Benton 166） and spray-dried to create powder, creating powder with particle sizes in the range of 10-40 μm. The materials were processed on a CO2 selective laser sintering （SLS） experimental machine. Mechanical properties of the PNCs were evaluated and the results were compared with the unfilled base polymer. Good dispersion of additives was achieved by solution blending, however the PA6 was degraded during the material preparation and spray drying process which resulted in the formation of porous structure and low strength. However the addition of 5 （wt%） nano particles in the PA6 has shown to increase strength by an average of 50-60%. Further work on powder preparation is required in order to fully realize these performance benefits.

Polymer Nanocomposites Used as Scaffolds for Bone Tissue Regeneration

Scaffolds are three-dimensional biocompatible structures that can mimic the properties of the extracellular matrix (ECM) of a given tissue, like mechanical support and bioactivity, which provides a platform for cellular adherence, proliferation and differentiation. Consequently, scaffolds are frequently used in tissue engineering with the intention of assisting the regeneration of a damaged tissue, and a major application in bone regeneration. An ideal scaffold needs to be biodegradable, biocompatible, and needs to match the biomechanical properties of bone. Polymers are widely used in this field because they fulfil the first two requirements. However, no polymeric material can achieve mechanical properties similar to the bone. For that reason, polymeric nanocomposites, which consist of ceramic/metallic nanoparticles dispersed in a polymer matrix, are being considered for bone scaffold fabrication in order to overcome this problem, since nanoparticles are known to improve composite mechanical strength, and enhance other properties.

Synthetic polymers:A review of applications in drilling fluids

With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complications.Currently,reagents based on modified natural polymers(which are naturally occurring compounds)and synthetic polymers(SPs)which are polymeric compounds created industrially,are widely used to prevent emerging complications in the drilling process.However,compared to modified natural polymers,SPs form a family of high-molecular-weight compounds that are fully synthesized by undergoing chemical polymerization reactions.SPs provide substantial flexibility in their design.Moreover,their size and chemical composition can be adjusted to provide properties for nearly all the functional objectives of drilling fluids.They can be classified based on chemical ingredients,type of reaction,and their responses to heating.However,some of SPs,due to their structural characteristics,have a high cost,a poor temperature and salt resistance in drilling fluids,and degradation begins when the temperature reaches 130℃.These drawbacks prevent SP use in some medium and deep wells.Thus,this review addresses the historical development,the characteristics,manufacturing methods,classification,and the applications of SPs in drilling fluids.The contributions of SPs as additives to drilling fluids to enhance rheology,filtrate generation,carrying of cuttings,fluid lubricity,and clay/shale stability are explained in detail.The mechanisms,impacts,and advances achieved when SPs are added to drilling fluids are also described.The typical challenges encountered by SPs when deployed in drilling fluids and their advantages and drawbacks are also discussed.Economic issues also impact the applications of SPs in drilling fluids.Consequently,the cost of the most relevant SPs,and the monomers used in their synthesis,are assessed.Environmental impacts of SPs when deployed in drilling fluids,and their manufacturing processes are identified,together with advances in SP-treatment methods aimed at reducing those impacts.Recommendations for required future research addressing SP property and performance gaps are provided.