Young's modulus of effective clay clusters in polymer nanocomposites

In polymer nanocomposites, the interfacial region plays a key role in the reinforcement of materials properties. Traditional two-phase micromechanical models usually ignore the contribution of such interfacial region to the overall materials properties. In this study, we use molecular dynamics simulation to determine the effective size and the Young's modulus of effective clay clusters which are regarded as basic building blocks in clay-based polymer nanocomposites. Two types of clay clusters are considered: one is fully exfoliated clay and another is partially exfoliated clay. The calculated Young's modulus of effective clay clusters can be used to predict the overall mechanical properties of clay-based polymer nanocomposites.     

Effect of PLA crystallization on the structure of biomimetic composites of PLA and clay

Composites of poly(lactic acid) (PLA) and organoclays with clay loadings of up to 80% were prepared as self‐supporting films using a doctor‐blading approach. Depending on the properties of the used organoclay, either intercalated nanocomposites or conventional composites were obtained. The incorporation of such high amounts of clay resulted in up to 10‐fold decrease in the water vapor transmission rate when compared to the pristine polymer. The effect of clay platelets on the crystallization of PLA chains was also studied; it was found that high amounts of clay hinder only the melt crystallization of the polymer, whereas cold crystallization proceeds as usual. On the other hand, the crystallization of PLA also influenced the composite structure by increasing the extent of intercalation of polymer between clay layers. This study thus shows that the change in the extent of clay‐polymer interactions is also an important factor in controlling nanocomposite structure, especially for high loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Predictions of micromechanics models for interfacial/interphase parameters in polymer/metal nanocomposites

In this paper, the polymer-metal interfacial/interphase parameters (PMIP) in polymer/metal nanocomposites are studied by modeling the mechanical properties. In this regard, the experimental results of yield strength, Young's modulus and elongation at break can be compared with the micromechanical models to evaluate the PMIP. The good agreement obtained between the experimental data of samples and the predictions confirms the applicability of models for polymer/metal nanocomposites. Many calculated parameters show the existence of a strong interphase in the reported samples. It is concluded that the fine morphology of nanoparticles and the strong interaction/adhesion at the polymer-metal interface can produce the significant PMIP in the polymer/metal nanocomposites.     

Structure,permeability, and rheology of supercritical CO2 dispersed polystyrene-clay nanocomposites

Improvement in clay dispersion and clay-polymer interfacial interactions are keys to producing superior nanocomposites. A supercritical CO₂ (scCO₂) processing method was utilized to pre-disperse commercial organic clays, for further solvent mixing with polystyrene (PS) to form nanocomposites with significant dispersion and interfacial enhancement. The effect of scCO₂ processing on clay pre-dispersion, and clay dispersion and interfacial interaction in nanocomposites were investigated. SEM and WAXD of the clays indicated that after scCO₂ processing the clays lose their long region ordered layer structure appreciably, associated with reduction in particle size. WAXD and TEM of the PS/clay nanocomposites showed that the polymer penetrated into the pre-dispersed clay, leading to a disordered intercalated/exfoliated structure with improved interfacial interaction rather than a disordered intercalated structure as seen with as-received clays. Relationships between those structures, rheological and barrier properties were investigated. The scCO₂-processed nanocomposites showed a plateau in the low-frequency storage modules and increased complex viscosity, each associated with significant clay dispersion in the nanocomposite. With only 1.09% volume fraction of clay, significant reduction (∼49%) of oxygen permeation was achieved.     

Synthesis and characterization of layer-aligned poly(vinyl alcohol)/graphene nanocomposites

Layer-aligned poly(vinyl alcohol)/graphene nanocomposites in the form of films are prepared by reducing graphite oxide in the polymer matrix in a simple solution processing. X-ray diffractions, scanning electron microscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis are used to study the structure and properties of these nanocomposites. The results indicate that graphene is dispersed on a molecular scale and aligned in the poly(vinyl alcohol) (PVA) matrix and there exists strong interfacial interactions between both components mainly by hydrogen bonding, which are responsible for the change of the structures and properties of the PVA/graphene nanocomposites such as the increase in T_g and the decrease in the level of crystallization.     

聚对苯二甲酸丁二醇酯/黏土纳米复合材料的研究进展

综述了聚对苯二甲酸丁二醇酯/黏土纳米复合材料研究的最新进展;从黏土表面改性剂的种类、黏土含量及其近、远程结构等方面总结了影响复合体系形态、黏弹特性、结晶行为的控制因素;探讨并评述了复合体系内部基体与黏土的多层次结构与其结晶、流变行为间的关系。     

Poly(ethylene terephthalate) ionomer based clay nanocomposites produced via melt extrusion

Poly(ethylene terephthalate) ionomer (PETI)/organically-modified montmorillonite clay (OMC) nanocomposites were prepared via melt extrusion. Sulfonated PET containing various incorporations of ionic comonomer and clay modifications were investigated. The random incorporation of ionic functionalities along the PET backbone enhances interactions between the matrix polymer and montmorillonite clay resulting in the creation of polymer-clay nanocomposites exhibiting a predominately exfoliated morphology. The morphology is correlated with mechanical properties and crystallization behavior. It is found that incorporation of clay into the random ionomers leads to increased mechanical properties and slower crystallization rates.     

Experimental and MD simulation study on the physical and mechanical properties of organically modified montmorillonite clay and compatibilized linear low density polyethylene nanocomposites

Understanding the interfacial interactions plays a key role in controlling mechanical and physical properties of polymer/clay nanocomposites (PCNs). In this work, the surface interactions between constituents of experimentally prepared PCNs which are the pristine linear low density polyethylene (PE) chains, PE compatibilizers, montmorillonite clay surface layer, and surfactants were studied quantitatively by employing molecular dynamics simulation technique. The interaction energy between the polymer and the clay was found to be inversely proportional with the volume of the surfactant which decreases the electrostatic interactions between the compatibilizer and the hydrophilic clay surface. However, the van der Waals (vdW) interactions between alkyl tails of surfactants and the PE chains increase with the tail length of the surfactants. The most attractive interaction was between the surfactant's head group and the clay surface. We showed that there existed fine balance between the electrostatic and vdW type forces on the stability and the enhanced properties of the PE–organoclay nanocomposites. Calculated interaction energies were then correlated to the experimentally measured mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45817.     

层状硅酸盐 /聚合物纳米复合材料的研究现状与前景

基于1996年以后的40余篇文献和作者的研究成果，综述了层状硅酸盐／聚合物纳米复合材料在制备技术、新品种、新性能、相关理论及应用等方面的最新研究进展，并总结出了以下观点：（1）粘土的有机化是制备纳米复合材料的第一关键要素，单体、预聚体、聚合物熔体与有机土的相容性是制备纳米复合材料的必要条件，外界剪切力可提供帮助；（2）剥离型结构最能体现层状硅酸盐／聚合物纳米复合材料的性能优势，是层状硅酸盐／聚合物纳米复合材料的制备方向；（3）聚合物熔体插层法为简单，是重要的发展方向，要形成剥离型结构，需要同时考虑热力学和动力学因素，基体或相容剂与层间环境的相容性要适中；（4）聚合物乳液共混共凝法有利于传统的制备方法，适合于具有乳液形成的聚合物；（5）在聚合物中原位生成硅酸盐片层的方法具有新意；（6）层状硅酸盐／聚合物纳米复合材料的主要特点是高刚性、高强度、高耐热性、高阻隔性、较好的阻燃性、质轻，目前，该的制备研究正向所有的聚合物品种扩展。汽车部件、包装材料将是层状硅酸盐／聚合物纳米复合材料先应用的两大领域；（7）层状硅酸盐／聚合物纳米复合材料的理论研究进展延慢。界面区状态以及结构－性能间的关系是理论研究的两个主题。     

EVOH/clay nanocomposites produced by melt processing

Ethylene‐vinyl alcohol copolymer(EVOH)/clay nanocomposites were prepared via a dynamic melt‐intercalation process. The phase morphology and the crystallization behavior of the nanocomposites were investigated, using DSC, DMTA, XRD and SEM. It was found that the treated clay content and dynamic processing time affect the viscosity of the EVOH/clay mixtures: higher clay contents and longer mixing times result in higher torque/viscosity levels. This is due to the increased interaction of the molten polar matrix (EVOH) with the treated organosilicate surface. Under the dynamic high shearing forces, the polymer penetrates the clay agglomerates/aggregates, intercalates within the organoclay galleries, and finally causes delaniination. Thermal analysis of the EVOH/clay nanocomposites showed that the melting temperature, crystallization temperature and heat of fusion of the EVOH matrix, sharply decrease with increasing both, the clay content and processing time. The intercalation level was characterized by X‐ray diffraction (XRD), which verified an increased gallery height. The DMTA spectra showed that longer processing times resulted in higher damping (E″ intensity) levels of the EVOH/clay composites, indicating higher fractions of the EVOH amorphous phase. However, no Tg changes were seen in spite of the high polymer/treated clay interaction levels, which may be attributed to a plasticizing effect of the low molecular weight organic cations.     

Interface adjustment between poly(ethylene terephthalate) and graphene oxide in order to enhance mechanical and thermal properties of nanocomposites

There is great interest in the use of graphene and derivatives in the production of polymer nanocomposites as it provides improvements in the properties of the materials to which they are associated. Such improvements depend heavily on filler dispersion and the interaction between the nanomaterials and the matrix. This work aimed to study the compatibility of graphene oxide (GO) with a poly(ethylene terephthalate) matrix. For this, graphite was modified using Hummers method, using reaction times of 3 and 6 h. The obtained GO was functionalized with amine, amide, and magnetite groups (FGO). The effects of the oxidation degree, functionalization and concentration of the nanofillers on the dispersion and consequently on the properties of the polymer nanocomposites were evaluated. The nanocomposites were synthesized by the solid–solid deposition method followed by the melt mixing technique. It was observed that lower concentrations of nanofiller associated with the lower degree of oxidation and functionalization improved the interaction of the nanofillers with the matrix, which resulted in better mechanical properties under tensile stresses for strain at break, maximum stress, Young's modulus and toughness. It was also observed that the glass transition and crystallization of nanocomposites increased due to a nucleating effect of the nanofillers.     

Development of simplified Tandon‐Weng solutions of Mori‐Tanaka theory for Young's modulus of polymer nanocomposites considering the interphase

The known Tandon‐Weng model originated from Mori–Tanaka theory commonly underestimates the Young's modulus of polymer nanocomposites containing spherical nanofillers. This phenomenon is attributed to disregarding the nanoscale interfacial interaction between polymer and nanoparticles, which forms a different phase as interphase in polymer nanocomposites. In this paper, the simplified Tandon‐Weng model is developed assuming interphase and the predictions of the developed model are compared with the experimental data. The calculations of the developed model completely agree with the experimental results at reasonable levels of interphase properties. Additionally, the effects of main material and interphase properties on the predictions of modulus are evaluated. The developed model predicts that a high‐content, thick, and strong interphase creates a high modulus in polymer nanocomposites. These logical observations demonstrate the correctness of the developed model for Young's modulus of polymer nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43816.     

Systematic study of interfacial interactions between clays and an ionomer

To study the interfacial interactions between an ionomer [poly(ethylene‐co‐acrylic acid) neutralized by zinc salts (PI)] and clays, PI–clay nanocomposites were prepared using a solution method. Two types of commercially available montmorillonite clays respectively K10 and KSF were used, and were modified with organic modifiers with chain lengths of 12–18 carbons. The interactions between the PI, clays, and modifiers were evaluated through study of the structure, morphology, and properties of the PI–clay nanocomposites. We found that the modifiers were successfully intercalated into the clay layers (Fourier transform infrared spectroscopy). The clay modified with a long‐chain agent showed an exfoliated nature in the nanocomposite. The thermal stability and storage modulus of PI were improved greatly by the addition of the clays, especially when the long‐chain modifier was used (thermogravimetric analysis and dynamic mechanical analysis). The differential scanning calorimetry results show that clay layers are inserted into the clusters because of solvent‐directed morphological evolution, so the transition of the ionic domains and the crystallinity of PI are changed. The interaction between PI, the modifier, and the silicate layer played an important role in the determination of the properties of the nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Isothermal crystallization kinetics and melting behavior of nylon/saponite and nylon/montmorillonite nanocomposites

DSC thermal analysis and X‐ray diffraction have been used to investigate the isothermal crystallization behavior and crystalline structure of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliating the layered silicates by subsequent polymerization. The DSC isothermal results reveal that introducing saponite into the nylon structure causes strongly heterogeneous nucleation induced change of the crystal growth process from a two‐dimensional crystal growth to a three dimensional spherulitic growth. But the crystal growth mechanism of nylon/montmorillonite nanocomposites is a mixed two‐dimensional and three‐dimensional spherulitic growth. The activation energy drastically decreases with the presence of 2.5 wt % clay in nylon/clay nanocomposites and then slightly increases with increasing clay content. The result indicates that the addition of clay into nylon induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). The correlation among crystallization kinetics, melting behavior, and crystalline structure of nylon/clay nanocomposites is also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2196–2204, 2004     

Largely enhanced crystallization of semi-crystalline polymer on the surface of glass fiber by using graphene oxide as a modifier

Interfacial crystallization of polymer on the surface of filler not only offers crystallography interest but also has a potential to improve the interfacial interaction, which is a key for the preparation of high-performance polymer/filler composites. In this work, a new method is proposed to improve the interfacial crystallization between semi-crystalline polymer and glass fiber (GF) by introducing graphene oxide (GO) to the surface of amorphous GF. The coating of GO on GF surface is realized via electrostatic self-assembling of the oppositely charged GO and amino coupling agent modified GF (GF-NH₂). After the thermal reduction of the coated GO (RGO), RGO coated GF (GF-RGO) is obtained. The interfacial crystallization of isotactic polypropylene (iPP) and poly(l-lactide) (PLLA) on the surface of raw GF, GF-NH₂, and GF-RGO are investigated using Polarized light microscope (PLM). It is found that raw GF and GF-NH₂ has almost no nucleation ability on the polymers crystallization. However, transcrystalline structure can be successfully induced at the polymers/GF-RGO interface, indicating a significantly improved nucleation ability of GF-RGO for polymer crystallization. This work could provide a new way to control interfacial crystallization, thus the interfacial adhesion of polymer/filler composites, and could also find a new application for GO as well.     

Crystallization behavior of nylon 6 nanocomposites

The crystallization behavior of nylon 6 nanocomposites formed by melt processing was investigated. Nanocomposites were produced by extruding mixtures of organically modified montmorillonite and molten nylon 6 using a twin screw extruder. Isothermal and non-isothermal crystallization studies involving differential scanning calorimetry (DSC) were conducted on samples to understand how organoclay concentration and degree of clay platelet exfoliation influence the kinetics of polyamide crystallization. Very low levels of clay result in dramatic increases in crystallization kinetics relative to extruded pure polyamide. However, increasing the concentration of clay beyond these levels retards the rate of crystallization. For the pure nylon 6, the rate of crystallization decreases with increasing the molecular weight as expected; however, the largest enhancement in crystallization rate was observed for nanocomposites based on high molecular weight polyamides; this is believed to stem from a higher degree of platelet exfoliation in these nanocomposites. Wide angle X-ray diffraction (WAXD) and DSC were further used to characterize the polymer crystalline morphology of injection molded nanocomposites. The outer or skin layer of molded specimens was found to contain only γ-crystals; whereas, the central or core region contains both the α and γ-forms. The presence of clay enhanced the γ-structure in the skin; however, the clay has little effect on crystal structure in the core. Interestingly, higher levels of crystallinity were observed in the skin than in the core for the nanocomposites, while the opposite was true for the pure polyamides. In general, increasing the polymer matrix molecular weight resulted in a lower degree of crystallinity in molded samples as might be expected.     

Free‐volume hole properties of two kinds thermoplastic nanocomposites based on polymer blends probed by positron annihilation lifetime spectroscopy

Two type of nanocomposites—an immiscible blend, high density polyethylene/polyamide 6 (HDPE/PA‐6) with organomodified clay, and a compatibilized blend, high density polyethylene grafted with acrylic acid/PA‐6 (PEAA/PA‐6) with organomodified clay—were prepared via melt compounding. X‐ray diffraction and transmission electron microscopy results revealed that the clay was intercalated and partially exfoliated. Positron annihilation lifetime spectroscopy has been utilized to investigate the free‐volume hole properties of two type of nanocomposites. The results show a negative deviation of free‐volume size in PEAA/PA‐6 blend, and a positive deviation in HDPE/PA‐6 blend, and I₃ has a greater negative deviation in compatibilized blend than in immiscible blend due to interaction between dissimilar chains. For nanocomposites based on polymer blends, in immiscible HDPE/PA‐6/organomodified clay system, the variation of free‐volume size with clay content is not obvious and the free‐volume concentration and fraction decreased. While in the case of compatibilized PEAA/PA‐6/organomodified clay nanocomposites, complicated variation of free‐volume properties due to interactions between two phases and organomodified clay was observed. And the interaction parameter β shows the interactions between polymers and organomodified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2463–2469, 2006     

Morphology and thermal properties of poly(L‐lactic acid)/organoclay nanocomposites

A modified clay was used to prepare poly(L ‐lactic acid)/clay nanocomposite dispersions. X‐ray diffraction and transmission electron microscopy experiments revealed that poly(L ‐lactic acid) was able to intercalate the clay galleries. IR spectra of the poly(L ‐lactic acid)/clay nanocomposites showed the presence of interactions between the exfoliated clay platelets and the poly(L ‐lactic acid). Thermogravimetric analysis and differential scanning calorimetry were performed to study the thermal behavior of the prepared composites. The properties of the poly(L ‐lactic acid)/clay nanocomposites were also examined as functions of the organoclay content. The exfoliated organoclay layers acted as nucleating agents, and as the organoclay content increased, the crystallization temperature increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007