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Block copolymers are recognized as a valuable platform for creating nanostructured materials. Morphologies formed by block copolymer self-assembly can be transferred into a wide range of inorganic materials, enabling applications including energy storage and metamaterials. However, imaging of the underlying, often complex, nanostructures in large volumes has remained a challenge, limiting progress in materials development. Taking advantage of recent advances in X-ray nanotomography, we noninvasively imaged exceptionally large volumes of nanostructured hybrid materials at high resolution, revealing a single-diamond morphology in a triblock terpolymer–gold composite network. This morphology, which is ubiquitous in nature, has so far remained elusive in block copolymer-derived materials, despite its potential to create materials with large photonic bandgaps. The discovery was made possible by the precise analysis of distortions in a large volume of the self-assembled diamond network, which are difficult to unambiguously assess using traditional characterization tools. We anticipate that high-resolution X-ray nanotomography, which allows imaging of much larger sample volumes than electron-based tomography, will become a powerful tool for the quantitative analysis of complex nanostructures and that structures such as the triblock terpolymer-directed single diamond will enable the generation of advanced multicomponent composites with hitherto unknown property profiles.

The reinforcement of polymer nanocomposites can be achieved through alignment or percolation of cellulose nanocrystals (CNCs). Here, we compare the efficacy of these reinforcement mechanisms in thermoplastic polyurethane (PU) elastomer nanocomposites containing thermally stable cotton CNCs. CNC alignment was achieved by melt spinning nanocomposite fibers, while a percolating CNC network was generated by solvent casting nanocomposite films with CNC contents up to 20 wt %. While in films both the CNCs and the PU matrix were entirely isotropic at all concentrations as confirmed by wide-angle X-ray scattering and birefringence analysis, the CNCs in the fibers exhibited a preferential orientation, which improved with increasing CNC concentration. Increasing the CNC concentration in the fibers reduces, however, the alignment of the PU chains, resulting in an entirely isotropic PU matrix at high CNC contents. The mechanical properties of films and fibers were evaluated using stress–strain measurements. Nanocomposite fibers with low CNC content exhibited superior stiffness, extensibility, and strength compared to the films, while the films displayed superior mechanical properties at high CNC concentrations. These findings are rationalized using common semiempirical models describing the reinforcing effects of CNC alignment in fibers (Halpin–Tsai) and CNC percolation in films (percolation model). The formation of a percolating CNC network leads to a stronger reinforcement than CNC alignment, as the reinforcing effect of the latter is limited by the comparably low aspect ratio of CNCs extracted from cotton. As a consequence, above the percolation threshold for cotton CNCs, isotropic nanocomposite PU films show a higher stiffness than aligned nanocomposite PU fibers.