Quantum mechanics simulation and experimental study of adhesive interaction and aggregation of carbon-silicate nanoparticles—reinforcing fillers of polymer composites

Nanoparticles are widely used as polymer composite-reinforcing additives—fillers. Understanding the interaction mechanisms and regularities responsible for nanoparticle aggregation is of great significance for elucidating the nature of reinforcing of polymer composites. The paper reports on quantum mechanics calculations and full-scale experimental study of adhesive interaction of carbon and silicate adsorption complexes (nanomodels of active filler particles of polymer composites). The quantum mechanics approach allowed describing the adhesive properties of particle aggregates reasoning from nanoscopic structure of their surface. The quantum mechanics data were checked for adequacy on schungite—a natural mineral containing carbon and silicate. Schungite microparticles were milled to nanosizes by colloidal grinding in various disperse liquid media (alcohol, acetone, water) and the structure and properties of aggregated schungite micro- and nanoparticles were studied; fractal analysis of their surface was performed. It is found that smaller aggregates of silicate and carbon particles with higher surface fractal dimension are formed in colloidal grinding with small molecular sizes of disperse media (in our case, ethanol or methanol) and this agrees with the data predicted by quantum mechanics calculations.     

Microstructure of stomaflex based magnetic elastomers

Stomaflex elastomers filled with two types of magnetic particles (nano- and micro-sized) were investigated. It was observed that doping with Fe₃O₄ nanoparticles and applying a magnetic field during the polymerisation process led to a significant change in the local structure of the elastomer. Decreases in the quasi-crystalline phase concentration, in the average size of the crystalline blocks, and in the ordering distance were observed after doping the elastomer with magnetite nanoparticles. After filling the polymer with Fe₃O₄ nanoparticles, yet the elastomer fractal dimension changes. For the elastomer filled with a large amount of Fe microparticles (75% particle concentration) a texture effect is observed, and this effect is larger for the samples polymerised in a magnetic field. At all microparticle concentrations, these elastomers exhibit surface fractal structure.     

Fracture of composites based on polyethylene and elastic particles

The composites based on low-density polyethylene with elastomer filling particles are studied. A fracture mechanism induced by the fracture of filler particles or their separation from the matrix polymer is revealed. The fracture of the composites is caused by the growth of formed rhombic pores. The natural relative elongation in a neck is shown to be an important characteristic of a polymer. If the relative elongation in a neck is lower than the strain of appearance of rhombic pores, they form at the stage of uniform tension after necking, and the composite remains plastic. If the relative elongation in a neck is higher than the strain of formation of rhombic pores, they nucleate during necking, and the material undergoes quasi-brittle fracture. Good adhesion between the matrix polymer and elastic particles hinders the appearance of rhombic pores in a neck and, thus, retains high deformation properties of the composites.     

Mechanical and dielectric properties of SEBS modified by graphite inclusion and composite interface

Tough and flexible dielectrics were prepared using graphite (G), a natural and low-cost resource, as filler in polystyrene-b-(ethylene-co-butylene)-b-polystyrene (SEBS) and maleinized SEBS (SEBS-MA) matrices. The disintegration of graphite in submicron particles was accomplished by the shear forces during the melt processing step and it was highlighted by atomic force microscopy. Simultaneous increase of tensile strain, strength and Young's modulus was noticed for SEBS/G and SEBS-MA/G composites compared to unfilled matrices, this remarkable feature being previously reported only for some nanocomposites. Moreover, an exponential variation of the dielectric permittivity with the volume fraction of G was obtained. Higher reinforcing efficiency and better dielectric properties were observed in SEBS-MA/G composites, compared to the corresponding SEBS/G composites, due to the stronger polymer–filler interface and better dispersion of graphite. This study brings new insights into nanolevel properties of SEBS composites and it opens new perspectives on high performance composites by using graphite instead of expensive graphene and efficient melt mixing process.     

Fractal and structural aspects of adhesion in particulate-filled polymer composites

Two types of composites based on poly(hydroxy ether) and graphite with various amounts of a filler have been investigated by various methods. The methods have been used to estimate the characteristics of adhesion and interfacial layer, including its thickness and tensile strength and interdependence between these values and adhesion. The results are treated on the basis of the theory of irreversible aggregation, cluster theory of the polymer structure and fractal analysis. It is established that all important characteristics of adhesion, interfacial layer and mechanical properties are interconnected with the difference between fractal dimensions of the surface of the aggregates of filler particles and of a polymer matrix, whose structure is distorted under the influence of the filler surface.     

Piezoelectrics based on a hybrid of piezoelectric matrix nano- and microcomposites

The physics and technology of a new class of efficient composite piezoelectrics are described. This material combines nanostructured and micropiezoelectric matrix composites. They consist of a polymer matrix, an insulating nanodimensional phase, and a microdimensional piezoelectric phase. It is shown that the nanostructuring of the near-surface region of polymer-PZT piezoelectric composites greatly improves their piezoelectric, mechanical, and electromechanical characteristics. A plausible mechanism underlying this effect is suggested.     

Acrylate Elastomer Toughened and UV Stabilized Polyoxymethylene

Acrylate elastomer (ACE) synthesized ourselves was mixed with antioxidative and UV stabilizer into polyoxymethylene (POM) matrices to investigate the effects of the ACE phase on the mechanical properties and UV stability of POM. For comparison, POM blended with same amount of TPU instead of ACE was used. Dispersion of the elastomer particles in POM matrices was investigated using SEM micrograph. Crystallinities of the specimen before and after UV ageing were also measured. The surface molecular weight and the mechanical properties of modified POM after UV ageing were determined. The result showed that excellent mechanical properties of the POM composites after UV‐irradiation could be obtained by blending with ACE.     

Multiscale Reinforcement of Polymers Combining Cellulosic Wood Pulp with Layered Silicate Nanoplatelets

Synergies resulting from the combination of discontinuous reinforcing elements at two different size scales are examined in two polymer types — rubbery matrices comprising acrylonitrile-co-butadiene (NBR) elastomer and a high density polyethylene plastic. The latter is derived from a recycled post-consumer waste stream that is upgraded by the reinforcement to compensate for any degradation experienced during prior use or impurities introduced during recycling. The two reinforcements are wood pulp at the microscale and exfoliating layered silicate clays at the nanoscale. Appropriate compatibilizing agents are employed to allow wetting of the reinforcement with the polymer matrix, promote dispersion and provide a strong interface. In general, the microscale elements provide mechanical strengthening in tension, while the nanoscale reinforcements enhance stiffening and reduce failure propagation by tearing. The use of natural reinforcements and recycled feedstocks imparts environmental acceptability to such formulations.     

Evolution of fractal particles in systems with conserved order parameter

Computer simulations of the evolution of fractal aggregates in systems with conserved order parameter are described in this work. The aggregates are generated by diffusion-limited aggregation. This model describes such important processes as annealing of dendrite inclusions in solids, healing of cracks in ceramics, temperature-induced transformations in composites, relaxation of rough surfaces, aging of colloid particles, etc. It is shown that the evolution in fractal media differs significantly from that occurring in initially homogeneous systems and leads to different values of the scaling exponent. A relationship between the fractal dimension, mechanism of relaxation, and scaling exponent was also derived.     

Phase Composition and Properties of Iron Nanocrystals and Clusters Embedded in MgO Matrix

Formation and stability of highly dispersed iron particles in crazed porous polymer matrices were studied. The iron–polymer composites obtained were characterized by different morphologies and dimensions of iron particles. The phase content of the iron constituent in a composite studied by Mössbauer spectroscopy was shown to depend on the type of the iron salt and the method of introduction of the initial reagents into a polymer.     

分形结构对随机取向烟尘团簇粒子光散射特性的影响

利用蒙特卡罗方法对不同分形维数和分形前向因子的随机取向烟尘团簇粒子的分形结构进行了仿真,采用离散偶极子近似（DDA）方法对随机取向烟尘团簇粒子的缪勒矩阵元进行了数值计算,并与球形粒子模型进行了比较,深入探讨了烟尘团簇粒子的分形维数和分形前因子对其散射特性的影响。研究表明,等效球形粒子的光散射特性与随机取向烟尘团簇粒子的光散射特性存在很大差别,并且此差别随着团簇粒子的分形维数以及分形前向因子的增大而减小;分形维数对表征团簇粒子散射特性的缪勒矩阵元的影响在一定散射角范围内均比较明显,分形前向因子对团簇粒子的缪勒矩阵元角分布的影响与分形维数的影响类似,不过其影响相对分形维数较弱。     

Interfacial modification for controlling silica–polysiloxane interactions and bonding in some elastomeric composites

Silica reinforcing fillers were generated using the sol-gel approach and their surfaces were modified using either a vinyl alkoxysilane (to provide permanent bonding to a host poly(dimethylsiloxane) elastomer), or a hemiacetal ester (to provide bonding that could be thermally ruptured). The surface areas of the fillers were measured by nitrogen absorption, and their morphologies, interfacial structures, and crosslinking to the elastomer were characterized by ultra small angle and small angle X-ray scattering, scanning electron microcopy, and Fourier-transform infrared spectroscopy. Increasing the amount of the silane coupling agent decreased silica domain sizes, with corresponding increases in surface area and stronger filler-polymer interactions. Vinyltrimethoxysilane had a larger effect than vinylmethyldimethoxysilane. The tensile moduli, tensile strengths, and degrees of toughness of the composites were determined using stress-strain measurements in elongation, both under near-equilibrium conditions and under continuous extension. The permanently bonded modifications gave composites with improved mechanical properties. Rupturing the hemiacetal ester bonding at 120-150°C gave some increase in ultimate stress, maximum elongation, and toughness, thus underscoring the importance of interactions or 'networking' between filler particles.     

Magnetostructural investigations of bulk nanostructured (Со–Р)<Subscript>100–<Emphasis Type="Italic">x</Emphasis></Subscript>Сu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> alloys

Magnetostructural investigations of bulk nanostructured Co–P/Cu composites prepared by dynamic compacting are performed. The magnetic microstructure of the obtained materials is characterized. It is shown that the use of composite particles allows us to create bulk materials with the structures and main magnetic properties of the initial powders.     

Electron Transfer through a One-Dimensional Fractal Structure

An adequate model of electron tunneling through a self-similar fractal potential (SFP) defined on a Cantor set is extended to a generalized Cantor set. It is demonstrated that, as in a specific case, the Schrödinger equation for the SFP is reduced to a functional equation for the transfer matrix which admits solutions of three types. Two of them are single-parameter solutions corresponding to SFP barriers and lacunas with arbitrary powers. In both cases, the transfer matrices are nonanalytic in the long-wavelength region and have fractal dimensionalities there. The third solution type includes a unique solution corresponding to the SFP barrier with fixed power for a given barrier width. The corresponding transfer matrix is analytic at the point k = 0. It is shown that generally the SFP possesses only the property of approximate scale invariance on the generalized Cantor set in the long- and short-wavelength regions. Only the limiting SFP, whose fractal dimensionality is equal to unity, possesses the property of rigorous scale invariance irrespective of its power. It is shown that SFPs with identical fractal dimensionalities but different lacunas are described by different transfer matrices.     

Nanocomposites of magnetic cobalt nanoparticles and cellulose

Polymeric matrices with stabilized metallic nanoparticles constitute an important class of nanostructured materials, because polymer technology allows fabrication of components with various electronic, magnetic and mechanical properties. The porous cellulose matrix has been shown to be a useful support material for platinum, palladium, silver, copper and nickel nanoparticles. In the present study, nanosized cobalt particles with enhanced magnetic properties were made by chemical reduction within a microcrystalline cellulose (MCC) matrix. Two different chemical reducers, NaBH₄ and NaH₂PO₂, were used, and the so-formed nanoparticles were characterized with X-ray absorption spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These experimental techniques were used to gain insight into the effect of different synthesis routes on structural properties of the nanoparticles. Magnetic properties of the nanoparticles were studied using a vibrating sample magnetometer. Particles made via the NaBH₄ reduction were amorphous Co-B or Co oxide composites with diminished ferromagnetic behaviour and particles made via the NaH₂PO₂ reduction were well-ordered ferromagnetic hcp cobalt nanocrystals.     

A numerical-analytical model for the characterization of composites reinforced by carbon nanotubes

A mixed model, numerical-analytical, is presented that allows one to predict the elastic properties of carbon nanotube (CNT)/polymer composites containing a random distribution of CNTs, while taking account of the curvature that they show when immersed in the polymer. This hybrid approach is a significant advance over micromechanical modeling and can be applied to all nanostructured composites.     

Microstructure,Interfacial Interactions,and Rheological Properties of PC/AES/Montmorillonite Composites

Polycarbonate (PC) and acrylonitrile–EPDM (ethylene/propylene/diene elastomer)–styrene ter‐polymer (AES) blends and PC/AES/organically modified montmorillonite (OMMT) composites were prepared at 20%, 40%, 50% by weight of AES and 3% by weight of OMMT. The microstructure, interfacial interactions, and rheological properties of the PC/AES blends and PC/AES/OMMT composites were studied systematically. X‐ray diffractometer (XRD) results reveal that the AES is easier to intercalate into OMMT than PC, and the content of AES has a little effect on the interlayer distance of OMMT. Wetting coefficient calculation indicates that OMMT distributes primarily at the interface of the polymer blend. Field emission scanning electron microscope (FE‐SEM) observation indicates that the phase morphology of PC/AES blends and PC/AES/OMMT composites is not influenced by the OMMT. However, linear rheological properties suggest that the addition of OMMT has a great effect on the linear rheological property.     

Structure and Properties of Polypropylene/Polyolefin Elastomer/Organic Montmorillonite Nanocomposites

The crystallinity, mechanical properties, and thermal stability of polypropylene (PP)/organic montmorillonite (OMMT) and PP/polyolefin elastomer (POE)/OMMT composites, with polypropylene-g-maleic anhydride/styrene (PPMS) as a compatibilizer for both, were compared. The results showed that the strong interaction between the clay platelets and compatibilizer, which were generated by the maleic anhydride (MAH), improved the compatibility of the polymer matrices with the OMMT. A unique lamellar, flocculated structure of OMMT was formed after introduction of the POE. The highly dispersed clay layers could act as nucleating agents, resulting in smaller spherulites and higher crystallization temperatures. Compared with pure PP, the PP/OMMT nanocomposite showed enhanced mechanical properties and thermal stability; however, the PP/POE/OMMT had the best impact toughness.     

Investigation of the structure of a polyimide modified by hyperbranched polyorganosiloxanes

Polymer composites based on polyimide and hyperbranched polyorganosiloxanes have been irradiated by oxygen plasma imitating exposure to atomic oxygen in low near-earth orbits. It is demonstrated that the irradiation of composites gives rise to the generation of silicon dioxide particles distributed over the volume of the polymer matrix, promoting enhanced resistance of the materials to the action of atomic oxygen. The structures of the samples are investigated via dielectric and IR spectroscopies. It has been ascertained that introduced modifiers lead to the formation of regions with an increased ordering of polyimide chains around filler particles.     

S-shaped current–voltage characteristics of polymer composite films containing graphene and graphene oxide particles

The resistive switching effects in composite films containing polyfunctional polymers, such as derivatives of carbazole (PVK), fluorene (PFD), and polyvinyl chloride (PVC), and also graphene particles (Gr) and graphene oxide (GO), the concentration of which in the polymer matrices varied in the range from 1 to 3 wt % corresponding to the percolation threshold in such systems, have been studied. The analysis of the elemental composition of the investigated composites by means of X-ray photoelectron spectroscopy have shown that the oxidation degree of Gr in GO is about 9 to 10%. It has been established that a sharp conductivity jump characterized by S-shaped current-voltage curves and the presence of their hysteresis occurs upon applying a voltage pulse to the Au/PVK (PFD; PVC): Gr (GO)/ITO/PET structures, where ITO is indium tin oxide, and PET is poly(ethylene terephthalate), with the switching time, t, in the range from 1 to 30 μs. The observed effects are attributed to the influence of redox reactions taking place on the Gr and GO particles enclosed in the polymer matrix, and the additional influence of thermomechanical properties of the polymer constituent of the matrix.