Cementitious binders amenable to extrusion‐based 3D printing are formulated by tailoring the fresh microstructure through the use of fine limestone powder or a combination of limestone powder and microsilica or metakaolin. Mixtures are proportioned with and without a superplasticizer to enable different particle packings at similar printability levels. A simple microstructural parameter, which implicitly accounts for the solid volume and inverse square dependence of particle size on yield stress can be used to select preliminary material combinations for printable binders. The influence of composition/microstructure on the response of pastes to extension or squeezing are also brought out. Extrusion rheology is used in conjunction with a phenomenological model to better understand the properties of significance in extrusion‐based printing of cementitious materials. The extrusion yield stress and die wall slip shear stress extracted from the model enables an understanding of their relationships with the fresh paste microstructure, which are crucial in selecting binders, extrusion geometry, and processing parameters for 3D printing.
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Summary We combined optical and atomic force microscopy to observe morphology and kinetics of microstructures (typically referred to as bees) that formed at free surfaces of unmodified Performance Graded (PG) 64‐22 asphalt binders upon cooling from 150°C to room temperature (RT) at 5°C min–1, and changes in these microstructures when the surface was terminated with a transparent solid (glass) or liquid (glycerol) overlayer. The main findings are: (1) at free binder surfaces, wrinkled microstructures started to form near the crystallization temperature (∼45°C) of saturates such as wax observed by differential scanning calorimetry, then grew to ∼5 µm diameter, ∼25 nm wrinkle amplitude and 10–30% surface area coverage upon cooling to RT, where they persisted indefinitely without observable change in shape or density. (2) Glycerol coverage of the binder surface during cooling reduced wrinkled area and wrinkle amplitude three‐fold compared to free binder surfaces upon initial cooling to RT; continued glycerol coverage at RT eliminated most surface microstructures within ∼4 h. (3) No surface microstructures were observed to form at binder surfaces covered with glass. (4) Submicron bulk microstructures were observed by near‐infrared microscopy beneath the surfaces of all binder samples, with size, shape and density independent of surface coverage. No tendency of such structures to float to the top or sink to the bottom of mm‐thick samples was observed. (5) We attribute the dependence of surface wrinkling on surface coverage to variation in interface tension, based on a thin‐film continuum mechanics model.
Lay Description Asphalt binder, or bitumen, is the glue that holds aggregate particles together to form a road surface. It is derived from the heavy residue that remains after distilling gasoline, diesel and other lighter products out of crude oil. Nevertheless, bitumen varies widely in composition and mechanical properties. To avoid expensive road failures, bitumen must be processed after distillation so that its mechanical properties satisfy diverse climate and load requirements. International standards now guide these mechanical properties, but yield varying long‐term performance as local source composition and preparation methods vary.
In situ diagnostic methods that can predict bitumen performance independently of processing history are therefore needed. The present work focuses on one promising diagnostic candidate: microscopic observation of internal bitumen structure. Past bitumen microscopy has revealed microstructures of widely varying composition, size, shape and density. A challenge is distinguishing bulk microstructures, which directly influence a binder's mechanical properties, from surface microstructures, which often dominate optical microscopy because of bitumen's opacity and scanning‐probe microscopy because of its inherent surface specificity. In previously published work, we used infrared microscopy to enhance visibility of bulk microstructure. Here, as a foil to this work, we use visible‐wavelength microscopy together with atomic‐force microscopy (AFM) specifically to isolatesurface microstructure, to understand its distinct origin and morphology, and to demonstrate its unique sensitivity to surface alterations. To this end, optical microscopy complements AFM by enabling us to observe surface microstructures form at temperatures (50°C–70°C) at which bitumen's fluidity prevents AFM, and to observe surface microstructure beneath transparent, but chemically inert, liquid (glycerol) and solid (glass) overlayers, which alter surface tension compared to free surfaces. From this study, we learned, first, that, as bitumen cools, distinctly wrinkled surface microstructures form at the same temperature at which independent calorimetric studies showed crystallization in bitumen, causing it to release latent heat of crystallization. This shows that surface microstructures are likely precipitates of the crystallizable component(s). Second, a glycerol overlayer on the cooling bitumen results in smaller, less wrinkled, sparser microstructures, whereas a glass overlayer suppresses them altogether. In contrast, underlying smaller bulk microstructures are unaffected. This shows that surface tension is the driving force behind formation and wrinkling of surface precipitates. Taken together, the work advances our ability to diagnose bitumen samples noninvasively by clearly distinguishing surface from bulk microstructure.