Additive manufacturing promises high flexibility and customized product design. Powder bed fusion processes use a laser to melt a polymer powder at predefined locations and iterate the scheme to build 3D objects. The design of flowable powders is a critical parameter for a successful fabrication process that currently limits the choice of available materials. Here, a bottom‐up process is introduced to fabricate tailored polymer‐ and composite supraparticles for powder‐based additive manufacturing processes by controlled aggregation of colloidal primary particles. These supraparticles exhibit a near‐spherical shape and tailored composition, morphology, and surface roughness. These parameters can be precisely controlled by the mixing and size ratio of the primary particles. Polystyrene/silica composite particles are chosen as a model system to establish structure–property relations connecting shape, morphology, and surface roughness to the adhesion within the powder, which is accessed by tensile strength measurements. The adhesive properties are then connected to powder flowability and it is shown that the resulting powders allow the formation of dense powder films with uniform coverage. Finally, successful powder bed fusion is demonstrated by producing macroscopic single layer specimens with uniform distribution of nanoscale silica additives.

Particulate materials with well-engineered properties are of key importance for many aspects in our daily life. Polymer powders with high flowability, for example, play a crucial role in the emerging field of powder-based additive manufacturing processes. However, the polymer- and composite material selection for these technologies is still limited. Here, we demonstrate the design of spherical polymethyl methacrylate (PMMA) and PMMA–SiO2 composite supraparticle powders with excellent powder flowability and tailored composition for powder-based additive manufacturing. Our process assembles these powders from the bottom up and affords a precise control over surface roughness and internal morphology via the choice of colloidal primary particles. We establish process-structure-property relationships connecting external spray-drying parameters and primary particle sizes with the resulting supraparticle roughness and, subsequently, with the macroscopic powder flowability and powder bed density. In a second step, we demonstrate the control of composition and internal morphology of PMMA–SiO2 composite supraparticles based on different mass mixings and diameter ratios of the two primary particle dispersions. Finally, we successfully apply the prepared supraparticle powders in powder bed additive manufacturing. The optimized flowability of the composite powders allows the production of two-layered square specimens with fusion between the individual layers and a uniform and tunable distribution of nanoscale SiO2 additives without requiring the addition of any flowing aids.

Additive manufacturing, in particular powder bed-based fabrication processes hold promise to revolutionize biomedical engineering for the ability to provide customized, functional implants, for example as bone replacement materials. However, providing functional powder particles that unify material requirements for biodegradable and bioactive biomaterials and process requirements to enable successful powder bed fusion remains an unmet challenge. Here, a supraparticle-based approach to create biodegradable poly(lactic acid) and composite powders for the additive manufacturing of bone replacement materials is introduced. Colloidal binary Ca-SiO 2 glasses and hydroxyapatite are incorporated as bioactive functional additives to support the formation of bone-like calcium phosphate. The supraparticle powders are prepared by a scalable spraydrying process, which offers control of particle size, shape, and composition. All process-relevant powder characteristics are analyzed as a function of composition and structure, including flowability, thermal, and melt rheological properties. The optimized supraparticle powders are successfully used in the process of laser powder bed fusion of polymers to prepare macroscopic specimens via additive manufacturing. It is demonstrated that the material combination of the composites provides relevant functional properties, including biodegradation and bioactivity. The process provides a flexible and adjustable toolbox for the design of functional powders toward biomedical additive manufacturing.

Analytical centrifugation is a versatile technique for the quantitative characterization of colloidal systems including colloidal stability. The recent developments in data acquisition and evaluation allow the accurate determination of particle...