High throughput methods for polymer nanocomposites research: Extrusion, NMR characterization and flammability property screening

A large number of parameters influence polymer-nanocomposite performance and developing a detailed understanding of these materials involves investigation of a large volume of the associated multi-dimensional property space. This multi-dimensional parameter space for polymer-nanocomposites consists of the obvious list of different material types under consideration, such as polymer and nano-additive, but also includes interphase surface chemistry, and processing conditions. This article presents combinatorial library design and high-throughput screening methods for polymer nanocomposites intended as flame-resistant materials. Here, we present the results of using a twin-screwn extruder to create composition-gradient library strips of polymer nanocomposites that are screened with a solid-state NMR method to rapidly evaluate the optimal processing conditions for achieving nanocomposite dispersion. In addition, we present a comparison of a new rapid Cone calorimetry method to conventional Cone calorimetry and to the gradient heat-flux flame spread method.     

有机磷氮系-蒙脱土/LDPE纳米复合材料的制备及阻燃性能

以三氯氧磷和新戊二醇等为原料, 合成了一种新型磷氮型季铵盐(PAHAC), 通过红外光谱(FTIR)、 核磁共振氢谱(1H-NMR)和高分辨质谱(HRMS)表征化合物结构。利用PAHAC与钠基蒙脱土(Na-MMT)离子交换反应制备有机磷氮系蒙脱土阻燃剂(PAHACMMT)。FTIR和X射线衍射(XRD)研究表明: PAHAC通过离子交换对蒙脱土进行了有机化改性, 经20%质量分数的PAHAC改性后的MMT(20%PAHAC-MMT)层间距增至1.87nm, 20%PAHACMMT的热分解温度在310℃以上。透射电镜(TEM)分析结果表明, 20%PAHACMMT经LDPE熔融插层, 形成了插层剥离型纳米复合材料。锥形量热测试结果表明有机磷氮系蒙脱土/LDPE纳米复合材料具有良好的阻燃性能, 其中20%PAHACMMT(7%)/LDPE的热释放速率峰值(PHRR)比LDPE降低了21%, 热释放总量(THR)下降了9.5%。炭层的扫描电镜(SEM)分析结果表明, 20%PAHACMMT/LDPE燃烧后能形成致密的炭层, 起到良好的阻燃作用。      

Evaluation and modelling of electrically conductive polymer nanocomposites with carbon nanotube networks

Superior electrical, thermal, and mechanical properties of carbon nanotubes (CNTs) have made them effective filler for multifunctional polymer nanocomposites (PNCs). In particular, electrically conductive PNCs filled with CNTs have been researched extensively. These studies aimed to increase the PNCs' electrical conductivity (σ) and to minimize the percolation thresholds (ϕ_c). In this work, we have developed an improved model to describe the CNT networks and thereby evaluate the PNCs' ϕ_c and σ. The new model accounts for the electrical conductance contributed by the continued CNT network across the boundary of adjacent representative volume elements. It more realistically represents the interconnectivity among CNTs and enhances the evaluation of the structure-to-property relationship of PNCs' σ.     

Nanoparticle assemblies in thin films of supramolecular nanocomposites

We demonstrated a versatile approach to obtain layered nanoparticle sheets with in-plane hexagonal order and 3-D ordered arrays of single nanoparticle chains in thin films upon blending nanoparticles with block copolymer (BCP)-based supramolecules. Basic understanding on the thermodynamic and kinetic aspects of the assembly process paved a path to manipulate these assemblies to meet demands in nanoparticle-based device fabrication and understand structure-property correlations.     

Nanoindentation in polymer nanocomposites

This article reviews recent literature on polymer nanocomposites using advanced indentation techniques to evaluate the surface mechanical properties down to the nanoscale level. Special emphasis is placed on nanocomposites incorporating carbon-based (nanotubes, graphene, nanodiamond) or inorganic (nanoclays, spherical nanoparticles) nanofillers. The current literature on instrumented indentation provides apparently conflicting information on the synergistic effect of polymer nanocomposites on mechanical properties. An effort has been done to gather information from different sources to offer a clear picture of the state-of-the-art in the field. Nanoindentation is a most valuable tool for the evaluation of the modulus, hardness and creep enhancements upon incorporation of the filler. It is shown that thermoset, glassy and semicrystalline matrices can exhibit distinct reinforcing mechanisms. The improvement of mechanical properties is found to mainly depend on the nature of the filler and the dispersion and interaction with the matrix. Other factors such as shape, dimensions and degree of orientation of the nanofiller, as well as matrix morphology are discussed. A comparison between nanoindentation results and macroscopic properties is offered. Finally, indentation size effects are also critically examined. Challenges and future perspectives in the application of depth-sensing instrumentation to characterize mechanical properties of polymer nanocomposite materials are suggested.     

Optical properties of polymer nanocomposites

Nanomaterials have emerged as an area of interest motivated by potential applications of these materials in light emitting diodes, solar cells, polarizers, light-stable colour filters, optical sensors, optical data communication and optical data storage. Nanomaterials are of particular interest as they combine the properties of two or more different materials with the possibility of possessing novel mechanical, electronic or chemical behaviour. Understanding and tuning such effects could lead to hybrid devices based on these nanocomposites with improved optical properties. We have prepared polymer nanocomposites of well-defined compositions and studied the optical properties of powders and their thin films. UV-vis absorption spectroscopy on nanocomposite powders and spectroscopic ellipsometry measurements on thin films was used to study the effect of interfacial morphology, interparticle spacing and finite size effects on optical properties of nanocomposites. Systematic shift in the imaginary part of the dielectric function can be seen with variation in size and fraction of the gold nanoparticle. The thickness of the film also plays a significant role in the tunability of the optical spectra.     

Molecular theories of polymer nanocomposites

Significant progress towards the development of microscopic predictive theories of the equilibrium structure, polymer-mediated interactions, and phase behavior of polymer nanocomposites has been made recently based on liquid state integral equation, density functional, and self-consistent mean field approaches. The basics of these three theoretical frameworks are summarized, and selected highlights of their recent applications discussed for spherical, nonspherical, and polymer-grafted nanoparticles dissolved in athermal and adsorbing concentrated solutions and homopolymer melts. The role of nanoparticle size, volume fraction, and interfacial cohesive interactions is emphasized, especially with regards to their influence on filler dispersion and spatial ordering via entropic depletion attraction, polymer adsorption-mediated steric stabilization, and local bridging of nanoparticles. Some of the many remaining theoretical challenges and open fundamental questions are summarized.     

Cyclic fatigue of polymer nanocomposites

This paper presents an experimental study on cyclic fatigue of two polymer nanocomposites in two common failure modes: mechanical failure in epoxy nanocomposites and thermal softening in polyamide (PA, nylon) 6 nanocomposites. For epoxy nanocomposites, the effects of hard (silica) and soft (rubber) nano-particles on un-notched samples under constant cyclic stress amplitude fatigue were studied. Hard particles were shown to increase but soft particles decrease the fatigue life of nanocomposites compared to unmodified epoxy. At the same stress amplitude, the extent of fatigue crack growth prior to fast fracture was largest in rubber nanocomposites and least in pure epoxy, reflecting the differences in their fracture toughness values. Ternary nanocomposites with both hard and soft (silica and rubber) particles were also investigated and their fatigue performances were compared to the binary nanocomposites. Further, the stress (σ_a) versus life (N_r) test data of pure epoxy and its binary and ternary nanocomposites are well described by Basquin’s law.PA6 nanocomposites exhibited fatigue failure due to thermal softening when the maximum local temperature of the specimens subjected to cyclic loading reached the glass transition temperature, T_g, of the material. Critical stress (σ_a) versus frequency (ω) envelopes for design against thermal failure were obtained for PA6/organoclay, PA6/POE-g-MA and PA6/pristine clay. Experimental results compared favorably with theoretical predictions.     

Quantitative equivalence between polymer nanocomposites and thin polymer films

The thermomechanical responses of polymers, which provide limitations to their practical use, are favourably altered by the addition of trace amounts of a nanofiller. However, the resulting changes in polymer properties are poorly understood, primarily due to the non-uniform spatial distribution of nanoparticles. Here we show that the thermomechanical properties of 'polymer nanocomposites' are quantitatively equivalent to the well-documented case of planar polymer films. We quantify this equivalence by drawing a direct analogy between film thickness and an appropriate experimental interparticle spacing. We show that the changes in glass-transition temperature with decreasing interparticle spacing for two filler surface treatments are quantitatively equivalent to the corresponding thin-film data with a non-wetting and a wetting polymer-particle interface. Our results offer new insights into the role of confinement on the glass transition, and we conclude that the mere presence of regions of modified mobility in the vicinity of the particle surfaces, that is, a simple two-layer model, is insufficient to explain our results. Rather, we conjecture that the glass-transition process requires that the interphase regions surrounding different particles interact.     

Functionalized graphene sheets for polymer nanocomposites

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.     

Supercritical fluid applications in polymer nanocomposites

Supercritical fluids have been used to synthesize and foam a variety of polymer nanocomposite materials. There have been significant advances in developing and characterizing nanoscale structures and using supercritical fluids to alter properties at the nanoscale. In this work we summarize these advances and discuss foam properties generated using supercritical carbon dioxide as well as relevant fundamental properties of the system.     

Properties of tin/plasma polymer nanocomposites

Thin composite layers (tin in plasma polymer matrix) were prepared in a stainless steel vacuum chamber. An RF powered magnetron with tin target was used to excite the discharge and to activate the monomer species (n-hexane). The gas mixture introduced comprised Ar and n-hexane vapours. The properties of the films and chemical composition were characterized by AFM (surface morphology), TEM and Electron tomography (bulk structure characterization), XPS and FTIR spectroscopy (chemical composition analyses). Current-voltage characteristics were measured to examine the electrical properties of the layers and their dependence on the deposition parameters.     

聚合物/MMT纳米复合材料的结晶性能

综述了尼龙/MMT、PP/MMT、PET/MMT等代表性的结晶性聚合物/MMT纳米复合材料结晶行为,分析了MMT的加入对聚合物结晶的影响,提出建立聚合物/MMT纳米复合材料宏观性能和微观结构之间的关系,并展望了未来的发展方向.     

Quantified stereological macrodispersion analysis of polymer nanocomposites

A quantified stereological characterization approach for polymer nanocomposite macrodispersion is presented. Three differently dispersed 1.0 wt.% polycarbonate/carbon nanofiber composites are studied with the analysis tool to quantitatively describe the differences in the nanocomposite microstructures. Strong trends were found describing the differences with observed agglomeration states. Established stereological functions were used with the observed agglomerate data to estimate the bulk macrodispersion states of the different systems. Error analysis was performed on the estimated bulk agglomeration states which revealed accurate or increased accuracy compared to observed data for the poor and medium dispersion systems studied. Through this characterization approach, a better understanding of nanocomposite macrodispersion states can be realized creating more effective property correlation and material behavior prediction.     

Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites

Owing to the improvement of properties including conductivity, toughness and permeability, polymer nanocomposites are slated for applications ranging from membranes to fuel cells. The enhancement of polymer properties by the addition of inorganic nanoparticles is a complex function of interfacial interactions, interfacial area and the distribution of inter-nanofiller distances. The latter two factors depend on nanofiller dispersion, making it difficult to develop a fundamental understanding of their effects on nanocomposite properties. Here, we design model poly(methyl methacrylate)-silica and poly(2-vinyl pyridine)-silica nanocomposites consisting of polymer films confined between silica slides. We compare the dependence of the glass-transition temperature (Tg) and physical ageing on the interlayer distance in model nanocomposites with the dependence of silica nanoparticle content in real nanocomposites. We show that model nanocomposites provide a simple way to gain insight into the effect of interparticle spacing on Tg and to predict the approximate ageing response of real nanocomposites.     

Nanoparticle interactions with the magnesium alloy matrix during physical deformation: Tougher nanocomposites

This study is aimed at understanding the toughness enhancing function of nanoparticles in magnesium nanocomposites, focussing on experimentally observed nanoparticle–matrix interactions during physical deformation. Al₂O₃ nanoparticles were selected for reinforcement purposes due to the well known affinity between magnesium and oxygen. AZ31/AZ91 (hybrid alloy) and ZK60A magnesium alloys were reinforced with Al₂O₃ nanoparticles using solidification processing followed by hot extrusion. In tension, each nanocomposite exhibited higher ultimate strength and ductility than the corresponding monolithic alloy. However, the increase in ductility exhibited by ZK60A/Al₂O₃ (+170%) was significantly higher than that exhibited by AZ31/AZ91/Al₂O₃ (+99%). The previously unreported and novel formation of high strain zones (HSZs, from nanoparticle surfaces inclusive) during tensile deformation is highlighted here as a significant mechanism supporting ductility enhancement in ZK60A/Al₂O₃ (+170% enhanced) and AZ31/AZ91/Al₂O₃ (+99% enhanced) nanocomposites. Also, ZK60A/Al₂O₃ exhibited lower and higher compressive strength and ductility (respectively) compared to ZK60A while AZ31/AZ91/Al₂O₃ exhibited higher and unchanged compressive strength and ductility (respectively) compared to AZ31/AZ91. Here, the previously unreported nanograin formation (recrystallization) during room temperature compressive deformation as a toughening mechanism in relation to nanoparticle stimulated nucleation (NSN) ability is also highlighted.     

C(60) reduces the flammability of polypropylene nanocomposites by in situ forming a gelled-ball network

The thermal and flame retardancy properties of polypropylene/fullerene (PP/C(60)) nanocomposites were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and cone calorimetry with the C(60) loading varied from 0.5 to 2% by weight. Dispersion of C(60) in the PP matrix was characterized by transmission electron microscopy (TEM) and optical microscopy (OM). TGA and DSC results showed that the presence of C(60) could remarkably enhance the thermal property and cone calorimeter measurements suggested that C(60) could to some extent reduce the flammability of PP, with a significant reduction in peak heat release rate and a much longer time to ignition. Furthermore, the larger the loading level of C(60), the better the flame retardancy property of PP/C(60) nanocomposites. The flame retardation mechanism and corresponding model were proposed with the help of rheological measurements, TEM and x-ray diffraction. C(60) reduced the flammability of PP by trapping free radicals in the gas phase and in situ forming a gelled-ball crosslink network to improve the flame retardancy of PP in the condensed phase. Finally, this suggested mechanism was supported by the results of advanced rheological extended systems (ARES), gel content, infrared spectrum, OM, and atomic force microscopy (AFM) measurements.     

Review on polymer/graphite nanoplatelet nanocomposites

Graphite nanoplatelets (GNPs) are a type of graphitic nanofillers composed of stacked 2D graphene sheets, having outstanding electrical, thermal, and mechanical properties. Furthermore, owing to the abundance of naturally existing graphite as the source material for GNPs, it is considered an ideal reinforcing component to modify the properties of polymers. The 2D confinement of GNPs to the polymer matrix and the high surface area make the GNP a distinctive nanofiller, showing superiorities in modification of most properties, compared with other carbon nanofillers. This review will summarize the development of polymer/GNP nanocomposites in recent years, including the fabrication of GNPs and its nanocomposites, processing issues, viscoelastic properties, mechanical properties, electrical and dielectric properties, thermal conductivity and thermal stability. The discussion of reinforcing effect will be based on dispersion, particle geometry, concentrations, as well as the 2D structures and exfoliation of GNPs. The synergy of GNPs with other types of carbon nanofillers used as hybrid reinforcing systems shows great potential and could significantly broaden the application of GNPs. The relevant research will also be included in this review.     

Magnetically actuable polymer nanocomposites for bioengineering applications

Methods are presented for creating biocompatible composites with magnetic functionality by incorporating magnetic nanoparticles in a biodegradable polymer matrix. A wide range of volume fractions for magnetic particle loading and therefore magnetization density are achievable. The nanoscale of the particles aids in achieving dispersion, so that variations in physical and chemical properties occur on scales much less than that of cells. Sufficient magnetization is achieved to enable actuation of the material, i.e., the generation of strains of biologically significant magnitudes using remotely applied magnetic fields. The magnitude of the actuation is demonstrated to enable fluid pumping and create local strains in cell aggregates that should be sufficient to stimulate cell growth and differentiation. The composite materials can be formed into random-pore scaffold materials with controlled porosity, pore shape, and pore connectivity. They can also be shaped by pressing, rolling, or drawing and joined by thermoplastic welding, so that ordered three-dimensional scaffold structures and various shell structures, such as tubes and toroids, can be fabricated. When the composite sheets are formed into tubes, the application of a moving magnetic field induces simulated peristalsis. When intestinal cells were seeded on the composite sheets, cells remained viable and grew rapidly in vitro.

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