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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.

By taking advantage of chirality transfer, nanonetwork with controlled chirality can be obtained from self-assembly., Nanonetwork-structured materials can be found in nature and synthetic materials. A double gyroid (DG) with a pair of chiral networks but opposite chirality can be formed from the self-assembly of diblock copolymers. For triblock terpolymers, an alternating gyroid (GA) with two chiral networks from distinct end blocks can be formed; however, the network chirality could be positive or negative arbitrarily, giving an achiral phase. Here, by taking advantage of chirality transfer at different length scales, GA with controlled chirality can be achieved through the self-assembly of a chiral triblock terpolymer. With the homochiral evolution from monomer to multichain domain morphology through self-assembly, the triblock terpolymer composed of a chiral end block with a single-handed helical polymer chain gives the chiral network from the chiral end block having a particular handed network. Our real-space analyses reveal the preferred chiral sense of the network in the GA, leading to a chiral phase.

Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni–porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873–1073 K. In addition, the porphyrin’s Ni–N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks., Carbon-based materials are promising alternatives to noble metal catalysts, but their structures are typically disordered and difficult to control. Here, the authors obtain ordered carbonaceous frameworks with advantageous electrocatalytic properties via the carbonization of nickel-containing porphyrin dimer networks.

Self-assembling structures and their dynamical processes in polymeric systems have been investigated using three-dimensional transmission electron microscopy (3D-TEM). Block copolymers (BCPs) self-assemble into nanoscale periodic structures called microphase-separated structures, a deep understanding of which is important for creating nanomaterials with superior physical properties, such as high-performance membranes with well-defined pore size and high-density data storage media. Because microphase-separated structures have become increasingly complicated with advances in precision polymerization, characterizing these complex morphologies is becoming increasingly difficult. Thus, microscopes capable of obtaining 3D images are required. In this article, we demonstrate that 3D-TEM is an essential tool for studying BCP nanostructures, especially those self-assembled during dynamical processes and under confined conditions. The first example is a dynamical process called order-order transitions (OOTs). Upon changing temperature or pressure or applying an external field, such as a shear flow or electric field, BCP nanostructures transform from one type of structure to another. The OOTs are examined by freezing the specimens in the middle of the OOT and then observing the boundary structures between the preexisting and newly formed nanostructures in three-dimensions. In an OOT between the bicontinuous double gyroid and hexagonally packed cylindrical structures, two different types of epitaxial phase transition paths are found. Interestingly, the paths depend on the direction of the OOT. The second example is BCP self-assemblies under confinement that have been examined by 3D-TEM. A variety of intriguing and very complicated 3D morphologies can be formed even from the BCPs that self-assemble into simple nanostructures, such as lamellar and cylindrical structures in the bulk (in free space). Although 3D-TEM is becoming more frequently used for detailed morphological investigations, it is generally used to study static nanostructures. Although OOTs are dynamical processes, the actual experiment is done in the static state, through a detailed morphological study of a snapshot taken during the OOT. Developing time-dependent nanoscale 3D imaging has become a hot topic. Here, the two main problems preventing the development of in situ electron tomography for polymer materials are addressed. First, the staining protocol often used to enhance contrast for electrons is replaced by a new contrast enhancement based on chemical differences between polymers. In this case, no staining is necessary. Second, a new 3D reconstruction algorithm allows us to obtain a high-contrast, quantitative 3D image from fewer projections than is required for the conventional algorithm to achieve similar contrast, reducing the number of projections and thus the electron beam dose. Combining these two new developments is expected to open new doors to 3D in situ real-time structural observation of polymer materials.

Scanning electron microscopy equipped with a focused ion beam (FIB-SEM) is a promising three-dimensional (3D) imaging technique for nano- and meso-scale morphologies. In FIB-SEM, the specimen surface is stripped by an ion beam and imaged by an SEM installed orthogonally to the FIB. The lateral resolution is governed by the SEM, while the depth resolution, i.e., the FIB milling direction, is determined by the thickness of the stripped thin layer. In most cases, the lateral resolution is superior to the depth resolution; hence, asymmetric resolution is generated in the 3D image. Here, we propose a new approach based on an image-processing or deep-learning-based method for super-resolution of 3D images with such asymmetric resolution, so as to restore the depth resolution to achieve symmetric resolution. The deep-learning-based method learns from high-resolution sub-images obtained via SEM and recovers low-resolution sub-images parallel to the FIB milling direction. The 3D morphologies of polymeric nano-composites are used as test images, which are subjected to the deep-learning-based method as well as conventional methods. We find that the former yields superior restoration, particularly as the asymmetric resolution is increased. Our super-resolution approach for images having asymmetric resolution enables observation time reduction.

Block copolymers synthesised in supercritical CO2 dispersion undergo in situ self-assembly which can result in a range of nanostructured microparticles. However, our previous study revealed that copolymers with different block combinations possessed different microphase separated morphologies at identical block volume fractions. In this paper, we follow up those initial observations. By examining the phase behaviour of a selection of structurally diverse block copolymers, we explore the structural factors which influence the conflicting self-assembly behaviours. The composition dependence of the morphology is found to be strongly related to the CO2-philicity of the second block relative to poly(methyl methacrylate) (PMMA). Whilst PMMA-b-poly(benzyl methacrylate) (PBzMA) and PMMA-b-poly(N, N-dimethylaminoethylmethacrylate) (PDMAEMA) phase behaviour follows traditional diblock copolymer phase diagrams, PMMA-b-poly(styrene) (PS) and PMMA-b-poly(4-vinyl pyridine) (P4VP), which comprise blocks with the greatest contrast in CO2-philicity, self-assemble into unexpected morphologies at several different block volume fractions. The morphology of these copolymers in the microparticulate form was found to revert to the predicted equilibrium morphology when the microparticles were re-cast as films and thermally annealed. These findings provide strong evidence that CO2 acts as a block-selective solvent during synthesis. The CO2-selectivity was exploited to fabricate various kinetically trapped non-lamellar morphologies in symmetrical PMMA-b-PS copolymers by tuning the ratio of polymer : CO2. Our data demonstrate that CO2 can be exploited as a facile process modification to control the self-assembly of block copolymers within particles.

New methods to visualize polymer morphologies in three-dimension (3D) in polymer science are reviewed. Here we concentrate on one of such 3D imaging technique, transmission electron microtomography (TEMT), and introduce some experimental studies using this novel technique. They are block copolymer morphologies during order-order transition between the two different morphologies and block copolymer thin film morphology also during morphological change due to confinement. Direct visualization of 3D structure of silica particle/rubber composite and related morphological analyses are shown. Subsequently, as a very hot topic of the 3D imaging, we show for the first time to characterize the morphological change in a silica particle/rubber composite upon stretching. It was found that the aggregates of silica particles were broken down upon stretching and many voids were generated near and between the silica particles. Local stress upon stretching inside the composite was inferred from the image intensity of the 3D reconstructed image. The local stress was found not only near the silica particles but also near the top of the voids. The observations indicated that the local stress increases the modulus, causing voids to form along the stretching direction. The thickness of the specimen after the stretching was also estimated from the 3D volume data, which turned out to be non-uniform and thinner than what is expected from the affine deformation. These experimental findings indicate that the rubber composite does not obey the assumption of the affine deformation at the nano-scale.

The three-dimensional (3D) morphology of particulate fillers embedded in a rubbery matrix was examined by transmission electron microtomography (TEMT). Two types of nanofillers, i.e., carbon black (CB) and silica (Si) nanoparticles, were used as the nanofillers. Although the CB and Si nanoparticles were difficult to distinguish by conventional transmission electron microscopy (TEM), they appeared different by TEMT; the CB and Si nanoparticles appeared to be hollow and solid particles in the cross-sectional images of the TEMT 3D reconstruction, respectively, demonstrating that TEMT itself provided a unique particle-discriminative function. The nanoparticles were found to form aggregates in the matrix. It is intriguing that each aggregate was made of only one species; not a single aggregate contained both the CB and Si nanoparticles. A particle-packing algorithm was developed to estimate the positions of each primary nanoparticle inside the aggregates.

Three-dimensional (3D) morphology of a polymer/clay nanocomposite, an organophilic montmorillonite (MMT) dispersed in poly(ethylene-co-vinylacetate) (EVA), was examined by transmission electron microtomography (TEMT). Using this technique, individual clay layers dispersed in the EVA matrix were clearly visualized. A volume fraction of the clay layers evaluated from the 3D reconstructed image agreed well with that calculated from the weight of the MMT component in the MMT/EVA system. The individual clay layers were digitally extracted by a newly developed 3D particle algorithm. A size distribution of the clay layers was directly obtained from the 3D reconstruction. Anisotropy of each clay layer was characterized by the determination of three semi-axes of an approximating ellipsoid with the same volume. One of the representative semi-axis of the ellipsoid was used to estimate average orientation of the MMT layers in the ultra-thin section used in the TEMT experiment. Thus, the combination of quantitative TE...

Fine metal particles (nanoparticles) stabilized on porous (polymeric) substrates can be considered as a model system of a high-performance catalyst. In the present study, the substrate was made using the periodic microphase-separated structure of a block copolymer as the template, and the Pd nanoparticles were formed inside the porous material by reduction of the Pd2+ ions with 1-propanol as the reductant. The three-dimensional morphology of such a polymer-Pd hybrid material was studied by transmission electron microtomography. The characteristic structural parameters of the hybrid, e.g., the penetration of the Pd nanoparticles into the polymer substrate, number density of the Pd nanoparticles, and size distribution of the Pd nanoparticles, were measured for the first time.

A sharp transition to pillar structure has been observed in simple sol-gel systems accompanying phase separation inside rectangular-sectioned open grooves which were fabricated on a silica glass chip. The structural variation was investigated using two contrastive systems; one with a rapid sol-gel reaction and the other with a sluggish reaction. In the slower system, transition from web-like bicontinuous structure to pillar structure, we call it as “web-to-pillar transition”, occurred when the bulk characteristic length Λ m exceeded the width of the groove D. On the other hand, the transition did not occur in the same condition in the faster system; it occurred when Λ m became much longer than D. A consistent formation mechanism model was also proposed using a relation between interfacial curvatures and pressure.

Methyl-siloxane gel and silica gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) and tetramethoxysilane (TMOS) were synthesized in two-dimensional (2D) confined spaces by inducing spinodal decomposition during the sol−gel transition. The resultant macroporous gel morphology was three-dimensionally examined by laser scanning confocal microscopy (LSCM), which revealed that the 2D confined gels have a layered structure. At the interface between MTMS- or TMOS-derived gel and a hydrophobic surface, the skin layer has formed by complete wetting by methylsiloxane and silica phase. In the near-surface region, a cylindrical columnar gel skeleton has formed only in the MTMS system. The volume fraction of gel phase oscillated near both hydrophobic and hydrophilic surfaces because of the attractive interactions between polymerizing siloxane and surfaces or shrinkage during aging stage.

Mesoscopic structures formed during an ordering process in thermodynamically unstable, isometric, binary molecular mixtures were explored by time-resolved scattering (TRS) and laser scanning confocal microscopy (LSCM). Three-dimensional (3D) bicontinuous structures, which were constructed for the first time by time-resolved LSCM, were found to have a sponge-like structure composed of two phases. The structure factor obtained by 3D Fourier transformation of the sponge was found to be identical to that obtained by TRS, confirming that the sponge truly reflects the structural entities evolving in the system. Furthermore, the sponge was shown for the first time to be theoretically predictable by using 3D computer simulations based on the time-dependent Ginzburg-Landau theory. The sponge was subjected to differential geometrical analysis: its Gaussian curvature K, mean curvature H, and their distributions were successfully determined for the first time. The result revealed that the sponge has hyperbolic interfaces with area-averaged curvatures satisfying ≅ 0 and that its interface has some deviations from a minimal surface. The sponge was found to be strikingly similar to that occurring in oil/water/surfactant systems at the hydrophile-lipophile-balance, though their characteristic length scales are diversely different (pm vs nm), implying universality of the sponge.

We observed shape recovery of a deformed droplet in an immiscible polymer matrix under large step strains using stereo microscopes from two directions. On application of a large step strain, a soft spherical droplet in a matrix with higher viscosity deformed to a flat ellipsoid. The stretch ratio of major axis of the flat ellipsoid was 5/4 times larger than that predicted from the affine deformation. The flat ellipsoid changed into a rod-like shape and then to a dumbbell, to an ellipsoid of revolution, and finally back to the sphere. The orientation angle between the major axis and shear direction did not change during the course of this shape recovery and was independent of the initial radius of the droplet. The time needed for the whole shape recovery got longer as the initial radius and the strain were increased. For a given step strain, the normalized interfacial area plotted against the stretch ratio fell onto a master curve irrespective of the initial radius of the undeformed droplet. It is shown that the deformed droplet reforms to the sphere after it passes through various shapes by reducing the interfacial area.

Determination of the three-dimensional (3D) shape of microphase-separated block copolymers (BCPs) is essential to investigate the “packing frustration” of the constituent blocks, which dominates th...

An overview is given of the three-dimensional microdomain structure of the star ABC composed of PS, PI, and PDMS with the arm-length (Mn) ratio of almost 1:1:1 (PS: 19.5K; PI: 20.7K; PDMS: 19.0K). In this case, strong repulsive interactions among the three different blocks yield a three-phase microdomain structure at room temperature.