In this study ceramic scaffolds of the bioresorbable and osteoconductive bioceramic β-tricalcium phosphate (β-TCP) were impregnated with the bioresorbable and ductile polymer poly(ε-caprolactone) (PCL) to investigate the influence of the impregnation on the mechanical properties of the porous composites. The initial β-TCP scaffolds were fabricated by the ice-templating method and exhibit the typical morphology of aligned, open, and lamellar pores. This pore morphology seems to be appropriate for applications as bone replacement material. The macroporosity of the scaffolds is mostly preserved during the solution-mediated PCL impregnation as the polymer was added only in small amounts so that only the micropores of β-TCP lamellae were infiltrated and the surface of the lamellae were coated with a thin film. Composite scaffolds show a failure behavior with brittle and plastic contributions, which increase their damage tolerance, in contrast to the absolutely brittle behavior of pure β-TCP scaffolds. The energy consumption during bending and compression load was increased in the impregnated scaffolds by (a) elastic and plastic deformation of the introduced polymer, (b) drawing and formation of PCL fibrils which bridge micro- and macrocracks, and (c) friction of ceramic debris still glued together by PCL. PCL addition also increased the compressive and flexural strength of the scaffolds. An explanatory model for this strength enhancement was proposed that implicates the stiffening of cold-drawn PCL present in surface flaws and micropores.
Porous materials, such as metal-organic frameworks emerge to solve important quests of our modern society, such as CO2 sequestration. Zeolitic Imidazolate Frameworks (ZIFs) can undergo a glass transition to form ZIF-glasses; they combine the liquid handling of classical glasses with tremendous potential for gas separations. Using millimeter-sized ZIF-62 single crystals and centimeter-sized ZIF-62-glass we demonstrate scalability and processability. Further, following the evolution of gas penetration into ZIF-crystals and ZIF-glasses by IR microimaging techniques enables to determine diffusion constants and changes to the pore architecture on the Angstrom-scale. The evolution of ZIF-glasses is observed in situ using a microscope heating stage. The pore-collapse during glass-processing is tracked by changes to density and volume of the glasses. Mass spectrometry investigates the crystal-to-glass transition and thermal processing ability.
in terms of deciphering structure-property relationships and the nonaffine nature of glass mechanical behavior, of computational and computer-assisted methods for accelerated materials discovery, and of physicochemical insight at glass formation and synthesis in unconventional types of materials. Despite this progress, significant questions remain as to the fundamental role of structural heterogeneity and its consequences for the predictability of mechanical properties underlying the many applications of glass. Today's challenge is to translate new understanding of the physics of disorder, glass chemistry, and surface mechanics into tools that enable future glass products with adapted elasticity, strength, and toughness. We will therefore consider fundamental advances in relation to emerging glass applications. While the aforementioned physical insights have mostly been obtained by computational simulation of model systems, and often through the examination of metallic glasses, we will here focus on glasses suitable for visible transparency, in particular silicate glasses, such as a representative of today's most prolific glass devices, ranging from ultrathin substrates to strong and visually transparent cover materials. We will further consider hybrid glasses and glass-like composite materials as emerging alternatives that may overcome the ubiquitous conflict between strength and toughness. [1] Glasses are materials that lack a crystalline microstructure and long-range atomic order. Instead, they feature heterogeneity and disorder on superstructural scales, which have profound consequences for their elastic response, material strength, fracture toughness, and the characteristics of dynamic fracture. These structure-property relations present a rich field of study in fundamental glass physics and are also becoming increasingly important in the design of modern materials with improved mechanical performance. A first step in this direction involves glass-like materials that retain optical transparency and the haptics of classical glass products, while overcoming the limitations of brittleness. Among these, novel types of oxide glasses, hybrid glasses, phase-separated glasses, and bioinspired glass-polymer composites hold significant promise. Such materials are designed from the bottom-up, building on structure-property relations, modeling of stresses and strains at relevant length scales, and machine learning predictions. Their fabrication requires a more scientifically driven approach to materials design and processing, building on the physics of structural disorder and its consequences for structural rearrangements, defect initiation, and dynamic fracture in response to mechanical load. In this article, a perspective is provided on this highly interdisciplinary field of research in terms of its most recent challenges and opportunities.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202109029.
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