Coarse-grained molecular dynamics simulation of nanofilled crosslinked rubber

A bead-spring model was applied to a crosslinked polymer with nanofillers for coarse-grained molecular dynamics simulation. Two nanofillers consisting 561 tightly connected beads and a crosslinked polymer with about 3000 beads were used as a simulation model. The strength of interactions between nanofiller and polymer based on the Lennard-Jones potential were varied. In order to investigate the effects of crosslinking and nanofiller on reinforcement, uniaxial elongation behavior was studied by coarse-grained molecular dynamics simulation with deformation function. From the uniaxial elongation simulation results and the analysis of polymer dynamics around nanofiller, it was confirmed that the degree of reinforcement depends on the strength of filler–polymer interaction, and one of the factors which influenced the stress was attributed to the existence of a low mobility phase around the nanofiller.     

Influence of nanometer scale particulate fillers on some properties of microfilled composite resin

The aim of this study was to evaluate the effect of different weight fractions of nanometer sized particulate filler on properties of microfilled composite resin. Composite resin was prepared by mixing 33 wt% of resin matrix to the 67 wt% of silane treated microfine silica particulate fillers with various fractions of nanometer sized fillers (0, 10, 15, 20, 30 wt%) using a high speed mixing machine. Test specimens made of the composites were tested with a three-point bending test with a speed of 1.0 mm/min until fracture. Surface microhardess (Vicker’s microhardness) was also determined. The volumetric shrinkage in percent was calculated as a buoyancy change in distilled water by means of the Archimedes principle. The degree of monomer conversion (DC%) of the experimental composites containing different nanofiller fractions was measured using FTIR spectroscopy. Surface roughness (Ra) was determined using a surface profilometer. Nanowear measurements were carried out using a nanoindentation device. The water uptake of specimens was also measured. Parameters were statistically analysed by ANOVA (P < 0.05). The group without nanofillers showed the highest flexural strength and modulus, DC% and Ra value. The group with 30% nanofillers had the highest water uptake and volumetric shrinkage. No significant difference was found in Vicker’s microhardness and the nanowear of the composites. The plain microfilled composite demonstrated superior properties compared to the composites loaded with nanofillers with the exception of surface roughness.     

High-performance nanocomposites based on polyetherketones

Polyetherketones, PEKs, are an important family of high-performance thermoplastic materials that display a unique combination of toughness, stiffness, thermooxidative stability, chemical and solvent resistance, flame retardancy, and retention of physical properties at high temperatures. A relevant step forward in the development of these materials has been the recent incorporation of nanofillers to extend their utility in advanced technological applications. This review provides an extensive overview of the research on PEK-based nanocomposites with a special emphasis on both carbon-based nanofillers, such as nanotubes or nanofibers, and inorganic nanoparticles. Nanocomposites can be fabricated by simple, low-cost conventional techniques such as extrusion and compression molding, generally combined with pre-processing stages involving mechanochemical treatments in organic solvents. Different strategies employed to efficiently incorporate carbon nanofillers into these matrices, including polymer functionalization, covalent grafting and nanofiller wrapping in compatibilizing systems are described. The analysis of the influence of the preparation and processing conditions as well as the nanofiller type, attributes and loading on the structure and properties of the resulting materials is also considered. Composites incorporating carbon nanofillers display remarkably improved thermal stability, electrical and thermal conductivity as well as mechanical property enhancements compared to the neat polymers. On the other hand, the incorporation of inorganic nanoparticles such as WS₂, SiO₂ or Al₂O₃ significantly enhances the tribological properties of the matrix, mainly the coefficient of friction and wear resistance. Finally, current and potential applications of these multifunctional nanocomposite materials in fields such as medicine, telecommunications, electronics, aerospace, automobile and chemical industries are described.     

A study on the curing and viscoelastic characteristics of melamine–urea–formaldehyde resin in the presence of aluminium silicate nanoclays

Low viscosity melamine–urea–formaldehyde (MUF) resin for wood impregnation was synthesized and mixed with layered silicate nanoclays. Ball-milling of the nanoclays was performed to have a better dispersion of the nanoclays into the MUF resin. The effect of nanofillers both milled and unmilled, on the curing and viscoelastic properties of the MUF was investigated, using differential scanning calorimetry and dynamical mechanical thermal analysis methods. Two exotherms were observed during the MUF curing process. The apparent activation energy was lowered for the first exotherm at lower temperature, while increased for the second exotherm, with the addition of nanoclays into the MUF. Ball-milling of nanofillers resulted in an increased apparent activation energy and longer gel time for the milled organophilic nanoclay/MUF, but shorter gel time and better dynamic mechanical properties of the milled hydrophilic nanofiller/MUF, as compared to the correspondingly unmilled nanofiller/MUF systems. The storage modulus of all the nanofiller/MUF resins was considerably increased as compared to the neat MUF resin. This improvement is, however, more obvious for the surface modified layered silicate/MUF system, due to more compatible functional-groups grafted onto the nanoclays, and stronger layered silicate/MUF matrix adhesion, thus better performances were observed for the resulting nanoclay/MUF composites.     

Comparing carbon nanotubes and graphene nanoplatelets as reinforcements in polyamide 12 composites

We investigate the influence of nanofillers including carbon nanotubes (CNTs) and graphene nanoplatelets on a thermoplastic engineering polymer, polyamide 12 (PA12). The comparison between these two important nanofillers as to how they influence the structure and properties of the polymer is systematically studied. The polymer-nanofiller composites were prepared using a twin-screw micro-extruder and the composite was thereafter hot pressed into thin films. The structure (using wide angle x-ray diffraction and differential scanning calorimetry) and properties (through tensile testing and conductivity measurement) of the thin films have been investigated. The composites incorporating surfactant showed the best CNT distribution and dispersion, causing an improvement of up to 80% in the toughness modulus over pure PA12. Electrical percolation could also be achieved at nanofiller concentrations of 1 to 2?wt%. In this study we observed that CNT fillers bring about more pronounced improvements in PA12 compared to graphene nanoplatelets, as far as mechanical and electrical properties are concerned.     

蒙脱土/碳纳米管组成对聚乙烯复合材料性能的影响

将改性的纳米蒙脱土(MMT)和官能化的多壁碳纳米管(MWCNTs)进行复合,然后负载TiCl4催化组分,制备出纳米载体Ziegler-Natta催化剂,最后进行乙烯原位聚合得到含有多维纳米材料的聚乙烯基复合材料。通过调控纳米载体中两种材料的组成,研究蒙脱土/碳纳米管组成对纳米复合材料性能的影响。结果表明:纳米蒙脱土、改性碳纳米管复合作为催化剂的载体,能够得到高活性的乙烯聚合催化剂。两种纳米材料组成的改变,会影响聚乙烯复合材料的力学性能。当多壁碳纳米管与蒙脱土比例为1∶1时,所得到的复合材料的拉伸强度为38.7MPa。     

Laser Surface Modification of Carbon Fiber Reinforced Composites

The removal of top resin layer is an essential task prior to adhesive bonding of carbon fiber reinforced polymer (CFRP) composites. This paper investigates the technical feasibility of using a low power continuous wave carbon dioxide laser for removing the top resin layer of CFRP without damaging the underlying fiber. The operating window and damaging threshold were experimentally determined. Irradiating the CFRP surface at a power of 14 W, scanning speed of 880 mm/sec, and a beam overlap of 25% provides an optimal thermal condition for removal of top resin layer. A finite element model was used to explain the removal mechanisms.     

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.     

橡胶纳米复合材料计算机模拟研究进展与挑战

总结了作者课题组采用分子动力学模拟研究橡胶纳米复合材料目前取得的主要进展,包括不同几何形状的纳米颗粒在橡胶基体中的分散机理、颗粒与橡胶分子链间的界面结合(聚合物玻璃化层是否存在)、颗粒对应力应变增强机理、碳纳米弹簧的引入对橡胶粘弹性的调控以及橡胶纳米复合材料非线性行为(Payne效应)产生的机理。模拟结果表明,存在一个最佳界面相互作用与接枝密度以实现纳米颗粒均匀分散;对于片状颗粒,在类似氢键界面相互作用时,存在聚合物玻璃化层。静态力学增强来自于两个方面:一是颗粒诱导分子链取向与排列,二是分子链吸附临近颗粒形成桥链在大变形下的有限链伸长。同时发现,碳纳米弹簧的加入会明显降低复合材料的滞后损失,并且得出纳米颗粒直接接触聚集与由分子链同时吸附多个颗粒成网对Payne效应非线性行为均有贡献。这些基础问题的澄清,将为制备动静态力学性能兼顾的橡胶纳米复合材料提供重要科学依据与理论指导,进而实现我国轮胎制品的高性能化与绿色化。最后针对橡胶纳米复合材料多层次多尺度结构与性能关系,简要评述了计算机模拟研究存在的挑战。     

Applicability of imaging time-of flight secondary ion MS to the characterization of solid-phase synthesized combinatorial libraries

We employ imaging time-of-flight secondary ion mass spectrometry to perform high-throughput analysis of solid-phase synthesized combinatorial libraries by acquiring mass spectra from arrays of polymer resin particles. To generalize this procedure to various types of resins and their associated chemical linkers, it is necessary to understand the dynamics associated with the analyte molecules during chemical pretreatment steps. Using stearic acid as a model compound, we examine the influence of three classes of linkers-acid or base labile linkers, a thermally labile linker, and a photochemically cleavable linker- all of which are used to anchor one end of the analyte to the polymer resin. With data obtained using secondary ion mass spectrometry, scanning electron microscopy, and X-ray photoelectron spectroscopy, we conclude that an effective treatment of the resin needs to include cleaving the linker and extracting the unbound analyte to the resin surface. We also demonstrate that the hydrophilicity of the polymeric constituents of a resin particle affects the experiments by changing the location of the analyte molecules during resin treatment. With this information, it is possible to utilize imaging TOF-SIMS to assay a range of material supports with assurance that high-quality spectra can be acquired.     

A simulation study on the effect of spring-shaped fillers on the viscoelasticity of rubber nanocomposite

Background/PurposeRubber nanocomposites have been widely used in many engineering fields due to their unique properties such as high elasticity and viscoelasticity. Much attention has been paid to the viscoelasticity of rubbers because it directly relates to the performance of the rubber products.MethodsBased on the micromechanical theory, the finite element method is used to analyze the effect of elastic modulus and volume content of spring-shape nanofillers on the dynamic viscosity of composites.ResultsThe simulation results show that there is an optimal elastic modulus of spring-shape nanofillers to make the loss factor a minimum. There is a threshold value of spring-shape nanofiller content for the dissipation energy density of composite.ConclusionThe elastic modulus of spring-shape nanofillers has a large effect on the loss factor of composites. The selection of elastic modulus of spring-shape nanofillers is critical for applications of composites. The efficiency of spring-shape nanofillers in reducing the dynamic viscosity of composites is so high that volume content of spring-shape nanofillers as low as 0.1% can greatly reduce the loss factor of composites with bonding interface.     

Monitoring the mechanical behaviour of electrically conductive polymer nanocomposites under ramp and creep conditions

Various amounts of carbon black (CB) and carbon nanofibres (CNF) were dispersed in an epoxy resin to prepare nanocomposites whose mechanical behaviour, under ramp and creep conditions, was monitored by electrical measurements. The electrical resistivity of the epoxy resin was dramatically reduced by both nanofillers after the percolation threshold (1 wt% for CB and 0.5 wt% for CNF), reaching values in the range of 10(3)-10(4) omega . cm for filler loadings higher than 2 wt%. Due to the synergistic effects between the nanofillers, an epoxy system containing a total nanofiller amount of 2 wt%, with a relative CB/CNF ratio of 90/10 was selected for the specific applications. A direct correlation between the tensile strain and the increase of the electrical resistance was observed over the whole experimental range, and also the final failure of the samples was clearly detected. Creep tests confirmed the possibility to monitor the various deformational stages under constant loads, with a strong dependency from the temperature and the applied stress. The obtained results are encouraging for a possible application of nanomodified epoxy resin as a matrix for the preparation of structural composites with sensing (i.e., damage-monitoring) capabilities.     

Relationships between phase morphology and deformation mechanisms in polymer nanocomposite nanofibres prepared by an electrospinning process

Relationships between phase morphology and mechanical deformation processes in various electrospun polymer nanocomposite nanofibres (PNCNFs) containing different types of one-, two-?and three-dimensional nanofiller have been investigated by transmission electron microscopy using in situ tensile techniques. From the study of the phase structure of electrospun PNCNFs, two morphological standard types are classified for the analysis of deformation mechanisms: the binary system (polymer matrix and nanofillers), and the ternary system (polymer matrix, nanofillers and nanopores on the fibres surface). According to these categories, deformation processes have been characterized, and different schematic models for these processes are proposed. The finding of importance in the present work is a brittle-to-ductile transition in polymer nanocomposite fibres during in situ tensile deformation processes. This unique feature in the deformation behaviour of electrospun PNCNFs provides an optimal balance of stiffness, strength and toughness for use as reinforcing elements in a polymer based composite of a new kind.     

石墨/酚醛树脂复合材料双极板的制备与性能

双极板是质子交换膜燃料电池的重要组成部分,石墨与聚合物的复合材料双极板是目前研究的重要方向。采用模压热固化二步法,以酚醛树脂为粘结剂、天然鳞片石墨为导电骨料、炭黑为添加剂制备了质子交换膜燃料电池用复合材料双极板。系统研究了不同种类石墨对石墨/酚醛树脂复合材料电性能和抗弯强度的影响。结果表明:以天然鳞片石墨为导电原料时,所制备的石墨/酚醛树脂双极板的性能最好;添加导电炭黑能有效提高石墨/酚醛树脂复合材料的电导率;在复合材料制备中加入4wt%的碳纤维,碳纤维-石墨/酚醛树脂复合材料的抗弯强度提高了29%;碳纤维表面液相氧化处理能有效提高纤维与基体间的结合强度,随着处理时间的延长与处理温度的升高,碳纤维-石墨/酚醛树脂复合材料的电导率和抗弯强度都有很大程度的提高;最终固化温度主要影响酚醛树脂的交联程度,随着最终固化温度的升高,酚醛树脂的交联程度增加,电导率增大,但抗弯强度有一定程度减小。     

Computational and experimental study of interfacial bonding of single-walled nanotube reinforced composites

In the development of nanotube reinforced polymer composites, one of the fundamental issues that scientists and engineers are confronting is the nanotube/polymer interfacial bonding, which will determine load transfer capability from the polymer matrix to the nanotube. In this paper, the interfacial bonding of single-walled nanotube (SWNT) reinforced epoxy composites was investigated using a combination of computational and experimental methods. The interfacial bonding was predicted using molecular dynamics (MD) simulations based on a cured epoxy resin model, which was constructed by incorporating three-dimensional cross-links formed during curing reaction. Based on the pullout simulations, the interfacial shear strength between the nanotube and the cured epoxy resin was calculated to be up to 75 MPa, indicating that there could be an effective stress transfer from the epoxy resin to the nanotube. In the experiments, single-walled nanotube reinforced epoxy composites were fabricated, characterized and analyzed. The uniform dispersion and good interfacial bonding of the nanotubes in the epoxy resin resulted in a 250–300% increase in storage modulus with the addition of 20–30 wt% nanotubes. These experimental results provided evidence of stress transfer in agreement with the simulation results.     

Photomechanical effects in a dye-doped polymer nanocomposite

Nile Red (NR) has been widely used as a microenvironmental probe since its luminescence characteristics depend strongly on medium polarity, viscosity, and hydrophobicity. The driving source for the internal motion of NR in rigid media is an absorbed photon that induces the molecule to rotate internally, causing the matrix deformed. Reversible (elastic) deformation and irreversible (plastic) deformation will influence the twisting dynamics in a different manner. In this work, we have investigated its excited state motion in a polymer nanocomposite, wherein polyvinyl alcohol (PVA) and nanodiamonds (NDs) were used as a matrix and a filler, respectively. PVA is a hydrophilic polymer having good chemical resistance, processability, and gel formation ability. Nanodiamond is a good candidate as a nanofiller for polymer composites. The elastic modulus of the polymer nanocomposite was measured by atomic force microscopy (AFM) nanoindentation and the emission lifetime of NR embedded in the polymer nanocomposite by time-resolved emission spectroscopy. Our results show that the fluorescence lifetime of NR is correlated well to the elastic modulus of polymer nanocomposite.     

Role of interfacial effects in carbon nanotube/epoxy nanocomposite behavior

The interfacial effects are critical to understand the nanocomposite behavior based on polymer matrices. These effects are dependent upon the morphology of carbon nanotubes, the type of used polymer and the processing technique. Indeed, we show that the different parameters, as the eventual surfactant use, the ultrasonic treatment and shear mixing have to be carefully examined, in particular, for nanotube dispersion and their possible alignment. A series of multiwalled nanotubes (MWNT) have been mixed with a regular epoxy resin under a controlled way to prepare nanocomposites. The influence of nanotube content is examined through helium bulk density, glass transition temperature of the matrix and direct current electrical conductivity measurements. These results, including the value of the percolation threshold, are analyzed in relationship with the mesostructural organization of these nanotubes, which is observed by standard and conductive probe atomic force microscopy (AFM) measurements. The wrapping effect of the organic matrix along the nanotubes is evidenced and analyzed to get a better understanding of the final composite characteristics, in particular, for eventually reinforcing the matrix without covalent bonding.     

Self-Compositing: A Efficient Method of Improving the Electrical Conductivity of Graphene Nanoplatelet/Thermosetting Resin Composites

Conductive composites based on thermosetting resins have broad applications in various fields. In this paper, a new self-compositing strategy is developed for improving the conductivity of graphene nanoplatelet/thermosetting resin composites by optimizing the transport channels. To implement this strategy, conventional graphene nanoplatelet/thermosetting resin is crushed into micron-sized composite powders, which are mixed with graphene nanoplatelets to form novel complex fillers to prepare the self-composited materials with thermosetting resins. A highly conductive compact graphene layer is formed on the surface of the crushed composite powders, while the addition of the micron-sized powder induces the orientation of graphene nanoplatelets in the resin matrix. Therefore, a highly conductive network is constructed inside the self-composited material, significantly enhancing the electrical conductivity. The composite materials based on epoxy resin, cyanate resin, and unsaturated polyester are prepared with this method, reflecting that the method is universal for preparing composites based on thermosetting resins. The highest electrical conductivity of the self-composited material based on unsaturated polyester is as high as 25.9 S m⁻¹. This self-compositing strategy is simple, efficient, and compatible with large-scale industrial production, thus it is a promising and general way to enhance the conductivity of thermosetting resin matrix composites.     

Polymerization Process and Morphology of Polyurethane/Vinyl Ester Resin Interpenetrating Polymer Networks

A series of polyurethane （PU）/vinyl ester resin （VER） simultaneous IPNs （interpenetrating polymer networks） with different component ratios and comonomers types introduced to VER were synthesized and the polymerization processes were traced by Fourier transform infrared spectroscopy （FTIR） to study the kinetics of IPNs and hydrogen bonding action within multi-component. Furthermore, the relationship of polymerization process with morphology was investigated in detail for the first time by the morphological information given by chemical action between two networks besides physical entanglement, atomic force microscope （AFM） observation and dynamic mechanical analysis （DMA）. The results indicated that the degree of hydrogen bonding （Xb,UT,%）, calculated from functional group conversional rate and fine structures gained from FT-IR spectra of two networks, were affected by PU/VER weight ratios and comonomer types of VER. The relationship of formation kinetics and morphology showed that the change of Xb,UT （%） values exhibited excellent consistency with that of phase sizes observed by AFM and detected by DMA.     

Depletion of water molecules during ethanol wet-bonding with etch and rinse dental adhesives

The treatment of demineralized dentin with ethanol has been proposed as a way to improve hydrophobic monomer penetration into otherwise water saturated collagen fibrils. The ethanol rinse is expected to preserve the fibrils from collapsing while optimizing resin constituent infiltration for better long term adhesion. The physico-chemical investigations of demineralized dentin confirmed objectively these working hypotheses. Namely, Differential Scanning Calorimetry (DSC) measurements of the melting point of water molecules pointed to the presence of free and bound water states. Unfreezable water was the main type of water remaining following a rinsing step with absolute ethanol. Two different liquid water phases were also observed by Magic Angle Spinning (MAS) solid state Nuclear magnetic Resonance (NMR) spectroscopy. Infrared spectra of ethanol treated specimens illustrated differences with the fully hydrated specimens concerning the polar carbonyl vibrations. Optical microscopy observations as well as scanning electron microscopy showed an improved dentin-adhesive interface with ethanol wet bonding. The results indicate that water can be confined to strongly bound structural molecules when excess water is removed with ethanol prior to adhesive application. This should preserve collagen from hydrolysis upon aging of the hybrid layer.