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This paper reviews recent advances and perspectives of electron microscopy and its application to polymer hierarchical structures. Of the various kinds of hierarchical polymer structures, we placed particular emphasis on polymer nanocomposites and polymer crystals based mainly on our recent results. In those nanocomposites, the chemical bonding between the nanometer-size fillers and rubber matrix, a key contributor to the mechanical properties of the material, has been investigated by combining scanning transmission electron microscopy (STEM) with electron energy-loss spectroscopy (EELS). The position-dependent EELS spectrum with high spatial resolution of STEM successfully provided revealed the presence/absence of the chemical bonds across the interface. The mechanical properties and fracture mechanism of nanocomposites have been studied by combining structural observations made using transmission electron microscopy (TEM) with simulations. They have been further investigated using in situ TEM with a newly designed stretching holder, in which morphological changes, including cavity formation, were visualized and analyzed in terms of local strain distribution. The fracture processes of nanocomposite have been observed at nanometer resolution. The fundamental reinforcement mechanisms have been elucidated from morphological studies of nanocomposites under tensile deformation and during the fracture process. Moreover, nano-diffraction imaging, a position-resolved electron diffraction imaging with STEM, has been applied to a polymer crystal to evaluate the orientation of lamellar crystals at nanometer resolution. All these recent successes with radiation-sensitive polymer materials stemmed from developments made in electron optics and super-sensitive cameras used for advanced electron microscopy.

This work reports a facile and versatile ring-opening metathesis polymerization of three- and four-armed star-shaped poly(epsilon-caprolactone) (PCL) macromonomers bearing a norbornenyl group at each chain end using Grubbs' third-generation catalyst under diluted condition to obtain graft polymers (GPs) comprising densely arrayed three- and four-armed cage-shaped grafted PCLs (GPCLs) with narrow dispersity (1.19-1.35) and a controllable number of cage repeating units up to 40 (molecular weight: similar to 320 000 g mol(-1)). The GPCLs were characterized using nuclear magnetic resonance spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. The cyclopolymerization proceeded via repetitive rapid intramolecular reactions to form cage-shaped units followed by slow intermolecular propagation. This synthesis was applicable to star-shaped poly(L-lactide), poly(trimethylene carbonate), and poly(ethylene glycol). Investigating the structure-property relationships regarding crystallization behavior, hydrodynamic diameter, and viscosity revealed that cage-shaped topological side chains reduced the chain dimensions and mobility compared to their linear and cyclic counterparts.

The mechanisms of electron irradiation damage to epoxy resin samples were evaluated using their electron diffraction patterns and electron energy–loss spectra. Their electron diffraction patterns consisted of three indistinct halo rings. The halo ring corresponding to an intermolecular distance of ∼6.4 Å degraded rapidly. Such molecular-scale collapse could have been caused by cross-linking between molecular chains. The degree of electron irradiation damage to the samples changed with the accelerating voltage. The tolerance dose limit of the epoxy resin estimated from the intensity of the halo ring was found to be improved at a higher accelerating voltage. Changes in low-loss electron energy–loss spectra indicated that the mass loss of the epoxy resin was remarkable in the early stage of electron irradiation.

Nanoparticle-filled rubber under tensile deformation was observed in situ by transmission electron microscopy (TEM), and the spatial distributions of the local maximum and minimum principal strains...

The degradation of a metal-polymer interface was studied in three dimensions using focused ion beam-scanning electron microscopy (FIB-SEM) with energy-dispersive X-ray spectroscopy. A brass-rubber interface, which is important for tires, was examined as an example of a metal-polymer interface. Brass-plated steel cords were embedded in rubber, which was then vulcanized. The brass-rubber interface was treated at 70 °C under 96% humidity for up to 14 days (a wet-heat aging treatment). FIB-SEM provided clear three-dimensional images of the adhesive layer consisting of brass (CuZn), CuxS, and ZnO/ZnS between the steel cords and rubber. During degradation, CuxS at the interfaces diffused into the rubber, resulting in the direct contact of bare steel with rubber. The lack of a substantial adhesive layer explained the degradation of mechanical properties after the wet-heat treatment. In addition, electron diffraction and electron energy loss spectroscopy revealed that the Cu2S crystals in the adhesive layer changed to crystal-like CuS during the degradation, which also caused a degradation of mechanical properties because a high Cu valence of x ≈ 2 in CuxS leads to stronger adhesion than a valence of x = 1.

The development of a strategy for the assembly of nanoscale building blocks, in particular, anisotropic nanoparticles, into desired structures is important for the construction of functional materials and devices. However, control over the orientation of rod-shaped nanoparticles on a substrate for integration into solid-state devices remains challenging. Here, we report a strategy for the fabrication of finely aligned gold nanorod (GNR) arrays using polymer (DNA) brushes as a nanoscale template. The gold nanorods modified with cationic surface ligands were electrostatically adsorbed onto the DNA brush substrates under various conditions. The orientational behavior of the GNRs was examined by spectral analyses and transmission electron microtomography (TEMT). As a result, we found several important factors, such as moderate interaction between GNRs and polymers and polymer densities on the substrate, related to the vertical alignment of GNRs on the substrates. We also developed a purification method to remove the undesired adsorption of GNRs onto the arrays. Finally, we have succeeded in the fabrication of extensive vertical GNR arrays of high quality via the easy bottom-up process.

It has been recognized that macromolecular chains can self-assemble into a hierarchical structure from lamellae to spherulites in bulk crystallization. However, little account has been taken of crystal symmetry effects on the hierarchical nanostructure in polymers under cylindrical confinement. In this research, a model polymer, nylon 6,12, most commonly occurring in the triclinic α phase, was chosen in order to demonstrate the effect of triclinic symmetry on the 2D-constrained polymer nanostructure. The self-arranging unit of nylon 6,12 takes various forms, including stems, unit cells, hydrogen-bonded sheets, lamellae and complex spherulites, which is an essential structural feature for investigating hierarchical nanostructure. The rod nanostructure in confinement was examined by cross-checking electron and X-ray diffraction techniques. It is found that the a* axis of the α-phase cell is inclined at about ±6–11° to the rod long axis within the a*b* plane around the c axis (c axis ⊥ rod long axis). The rotation of the a*b* plane most likely results from the impact of the triclinic symmetry on the molecular chain packing under 2D confinement. A mechanism for this a*b* plane tilting is proposed.

In order to explain or predict the macroscopic mechanical properties of polymer composites with complex nanostructures, atomic force microscopy (AFM)-based nanomechanics is one of the most appropriate tools because the local mechanical properties can be obtained by it. However, automatic force curve analysis based on contact mechanics would mislead us to the wrong conclusion. The purpose of this study is to elucidate this point by applying AFM nanomechanics on a carbon black (CB)-reinforced isoprene rubber (IR). The CB aggregates underneath the rubber surface prevent us from quantitatively evaluating the ratio of CB and interfacial polymer region (IPR), which is an important parameter to determine the macroscopic mechanical properties. In order to overcome this problem, transmission electron microtomography was incorporated to investigate the 3D structure in the same field of view as AFM nanomechanics. As a result, it was found that there are buried structures that do not appear in the AFM topographic image. In addition, we were able to reveal the existence of a force curve with an inflection point, which is characteristic of such "false" IPRs. To put it another way, we evidenced the existence of true IPRs for the first time by combining these state-of-the-art techniques.

Polarized optical microscopy (POM) and transmission electron microscopy (TEM) are widely used for imaging polymer spherulite structures. TEM provides nanometer resolution to image small spherulites of sub-micrometer in diameter, while POM is more suitable for observing large spherulites. However, high-resolution images with a large field of view are challenging to achieve due to the deformations of ultrathin sectioned samples used for TEM observations. In this study, we demonstrated that correlative light and electron microscopy (CLEM) combining POM and TEM could effectively characterize the spherulite structures in a wide range from nanometer to several hundred micrometers that neither TEM nor POM alone could cover. Furthermore, the deformations of the TEM ultrathin sections were corrected by referencing to the POM images at the same position of the sample, and large-area TEM images without deformations were successfully produced. The spherulite structures of poly(ʟ-lactic acid) were successfully analyzed using CLEM and TEM in a wide range of spatial scales at the same field of view. The large-area TEM image (250 µm × 250 µm), consisting of 702 TEM images stitched together, was subjected to machine learning to extract the essential structural information of spherulites. Analysis using the convolutional neural network, a well-known algorithm You Only Look Once (YOLO), demonstrated that it was practical to accurately obtain the diameter distribution and the space-filling factor (relative crystallinity) of the spherulites. This study presents a new approach for acquiring high-resolution images with a large field of view and processing the images at a fast speed.

In this work, the authors succeed in direct visualization of the network structure of synthetic hydrogels with transmission electron microscopy (TEM) by developing a novel staining and network fixation method. Such a direct visualization is not carried out because sample preparation and obtaining sufficient contrast are challenging for these soft materials. TEM images reveal robust heterogeneous network architectures at mesh size scale and defects at micro-scale. TEM images also reveal the presence of abundant dangling chains on the surface of the hydrogel network. The real space structural information provides a comprehensive perspective that links bulk properties with a nanoscale network structure, including fracture, adhesion, sliding friction, and lubrication. The presented method has the potential to advance the field.

Hydrogels are promising materials for several applications, including cell scaffolds and artificial load-bearing substitutes (cartilages, ligaments, tendons, etc.). Direct observation of the nanoscale polymer network of hydrogels is essential in understanding its properties. However, imaging of individual network strands at the molecular level is not achieved yet due to the lack of suitable methods. Herein, for the first time, we developed a novel mineral-staining method and network fixation method for transmission electron microscopy observation to visualize the hydrogel network in its unperturbed conformation with nanometer resolution. Surface network observation indicates that the length of surface dangling chains, which play a major role in friction and wetting, can be estimated from the gel mesh size. Moreover, bulk observations reveals a hierarchical formation mechanism of gel heterogeneity. These observations have the great potential to advance gel science by providing comprehensive perspective that link bulk gel properties with nanoscale.

Block copolymers (BCPs) under nanoscale confinement can self-assemble to form novel nanostructures that are not available in the bulk state. Particularly, the ordering process of block copolymers a...

In fibers spun from polymer solutions, we investigated self-organization of ordered shish kebabs via the cascade evolution of various dissipative structures through multistep phase transitions at multiple length scales. We used transmission electron microtomography to discover for the first time crystalline fibrils with diameters of ∼10 nm that orthogonally bridge neighboring kebabs epitaxially overgrown from shishs. The fibrils evolved during the late-stage self-organization processes of the shish kebabs. The fibrils were classified as completely bridging fibrils and pairs of broken fibrils facing each other; the broken fibrils were formed by the following two steps, first by the flow-induced burst of the bridging domains driven by Laplace pressure and subsequent crystallization involved in the burst domains. The bridging and broken fibrils were observed at interkebab distances smaller and larger than the critical length of ∼80 nm, respectively. The bridging fibrils and the cores of the broken fibrils ha...

To effectively archive configuration data during molecular dynamics (MD) simulations of polymer systems, we present an efficient compression method with good numerical accuracy that preserves the topology of ring-linear polymer blends. To compress the fraction of floating-point data, we used the Jointed Hierarchical Precision Compression Number - Data Format (JHPCN-DF) method to apply zero padding for the tailing fraction bits, which did not affect the numerical accuracy, then compressed the data with Huffman coding. We also provided a dataset of well-equilibrated configurations of MD simulations for ring-linear polymer blends with various lengths of linear and ring polymers, including ring complexes composed of multiple rings such as polycatenane. We executed 109 MD steps to obtain 150 equilibrated configurations. The combination of JHPCN-DF and SZ compression achieved the best compression ratio for all cases. Therefore, the proposed method enables efficient archiving of MD trajectories. Moreover, the publicly available dataset of ring-linear polymer blends can be employed for studies of mathematical methods, including topology analysis and data compression, as well as MD simulations.