Digital manufacturing of personalised footwear with embedded sensors.

The strong clinical demand for more accurate and personalized health monitoring technologies has called for the development of additively manufactured wearable devices. While the materials palette for additive manufacturing continues to expand, the integration of materials, designs and digital fabrication methods in a unified workflow remains challenging. In this work, a 3D printing platform is proposed for the integrated fabrication of silicone-based soft wearables with embedded piezoresistive sensors. Silicone-based inks containing cellulose nanocrystals and/or carbon black fillers were thoroughly designed and used for the direct ink writing of a shoe insole demonstrator with encapsulated sensors capable of measuring both normal and shear forces. By fine-tuning the material properties to the expected plantar pressures, the patient-customized shoe insole was fully 3D printed at room temperature to measure in-situ gait forces during physical activity. Moreover, the digitized approach allows for rapid adaptation of the sensor layout to meet specific user needs and thereby fabricate improved insoles in multiple quick iterations. The developed materials and workflow enable a new generation of fully 3D printed soft electronic devices for health monitoring.

Complex Living Materials Made by Light-Based Printing of Genetically Programmed Bacteria.

Living materials with embedded microorganisms can genetically encode attractive sensing, self-repairing, and responsive functionalities for applications in medicine, robotics, and infrastructure. While the synthetic toolbox for genetically engineering bacteria continues to expand, technologies to shape bacteria-laden living materials into complex 3D geometries are still rather limited. Here, it is shown that bacteria-laden hydrogels can be shaped into living materials with unusual architectures and functionalities using readily available light-based printing techniques. Bioluminescent and melanin-producing bacteria are used to create complex materials with autonomous chemical-sensing capabilities by harnessing the metabolic activity of wild-type and engineered microorganisms. The shaping freedom offered by printing technologies and the rich biochemical diversity available in bacteria provides ample design space for the creation and exploration of complex living materials with programmable functionalities for a broad range of applications.

Living materials made by 3D printing cellulose-producing bacteria in granular gels.

Bacterial cellulose is an attractive resource for the manufacturing of sustainable materials, but it is usually challenging to shape it into elaborate three-dimensional structures. Here, we report a manufacturing platform for the creation of complex-shaped cellulose objects by printing inks loaded with bacteria into a silicone-based granular gel. The gel provides the viscoelastic behavior necessary to shape the bacteria-laden ink in three dimensions and the gas permeability required to sustain cellular growth and cellulose formation after the printing process. Using Gluconacetobacter xylinus as model cellulose-producing bacteria, we study the growth and the mechanical properties of cellulose fiber networks obtained upon incubation of the printed inks. Diffusion processes within the ink were found to control the growth of the cellulose structures, which display mechanical properties within the range expected for conventional hydrogels. By keeping the bacteria alive in the printed object, we produce living materials in complex geometries that are able to self-regenerate their cellulose fiber network after damage. Such living hydrogels represent an enticing development towards functional materials with autonomous self-healing and self-regenerating capabilities.

Three-dimensional printing of photonic colloidal glasses into objects with isotropic structural color.

Structural color is frequently exploited by living organisms for biological functions and has also been translated into synthetic materials as a more durable and less hazardous alternative to conventional pigments. Additive manufacturing approaches were recently exploited for the fabrication of exquisite photonic objects, but the angle-dependence observed limits a broader application of structural color in synthetic systems. Here, we propose a manufacturing platform for the 3D printing of complex-shaped objects that display isotropic structural color generated from photonic colloidal glasses. Structurally colored objects are printed from aqueous colloidal inks containing monodisperse silica particles, carbon black, and a gel-forming copolymer. Rheology and Small-Angle-X-Ray-Scattering measurements are performed to identify the processing conditions leading to printed objects with tunable structural colors. Multimaterial printing is eventually used to create complex-shaped objects with multiple structural colors using silica and carbon as abundant and sustainable building blocks.

Self-Grown Bacterial Cellulose Capsules Made through Emulsion Templating.

Microcapsules made of synthetic polymers are used for the release of cargo in agriculture, food, and cosmetics but are often difficult to be degraded in the environment. To diminish the environmental impact of microcapsules, we use the biofilm-forming ability of bacteria to grow cellulose-based biodegradable microcapsules. The present work focuses on the design and optimization of self-grown bacterial cellulose capsules. In contrast to their conventionally attributed pathogenic role, bacteria and their self-secreted biofilms represent a multifunctional class of biomaterials. The bacterial strain used in this work, Gluconacetobacter xylinus, is able to survive and proliferate in various environmental conditions by forming biofilms as part of its lifecycle. Cellulose is one of the main components present in these self-secreted protective layers and is known for its outstanding mechanical properties. Provided enough nutrients and oxygen, these bacteria and the produced cellulose are able to self-assemble at the interface of any given three-dimensional template and could be used as a novel stabilization concept for water-in-oil emulsions. Using a microfluidic setup for controlled emulsification, we demonstrate that bacterial cellulose capsules can be produced with tunable size and monodispersity. Furthermore, we show that successful droplet stabilization and bacterial cellulose formation are functions of the bacteria concentration, droplet size, and surfactant type. The obtained results represent the first milestone in the production of self-assembled biodegradable cellulose capsules to be used in a vast range of applications such as flavor, fragrance, agrochemicals, nutrients, and drug encapsulation.

Sustainable and Biodegradable Wood Sponge Piezoelectric Nanogenerator for Sensing and Energy Harvesting Applications.

Developing low-cost and biodegradable piezoelectric nanogenerators is of great importance for a variety of applications, from harvesting low-grade mechanical energy to wearable sensors. Many of the most widely used piezoelectric materials, including lead zirconate titanate (PZT), suffer from serious drawbacks such as complicated synthesis, poor mechanical properties (e.g., brittleness), and toxic composition, limiting their development for biomedical applications and posing environmental problems for their disposal. Here, we report a low-cost, biodegradable, biocompatible, and highly compressible piezoelectric nanogenerator based on a wood sponge obtained with a simple delignification process. Thanks to the enhanced compressibility of the wood sponge, our wood nanogenerator (15 × 15 × 14 mm3, longitudinal × radial × tangential) can generate an output voltage of up to 0.69 V, 85 times higher than that generated by native (untreated) wood, and it shows stable performance under repeated cyclic compression (≥600 cycles). Our approach suggests the importance of increased compressibility of bulk materials for improving their piezoelectric output. We demonstrate the versatility of our nanogenerator by showing its application both as a wearable movement monitoring system (made with a single wood sponge) and as a large-scale prototype with increased output (made with 30 wood sponges) able to power simple electronic devices (a LED light, a LCD screen). Moreover, we demonstrate the biodegradability of our wood sponge piezoelectric nanogenerator by studying its decomposition with cellulose-degrading fungi. Our results showcase the potential application of a wood sponge as a sustainable energy source, as a wearable device for monitoring human motions, and its contribution to environmental sustainability by electronic waste reduction.

Conformal Bacterial Cellulose Coatings as Lubricious Surfaces.

We report a versatile method to form bacterial cellulose coatings through simple dip-coating of 3D objects in suspensions of cellulose-producing bacteria. The adhesion of cellulose-secreting bacteria on objects was promoted through surface roughness and chemistry. Immobilized bacteria secreted highly porous hydrogels with high water content directly from the surface of a variety of materials. The out-of-plane orientation of cellulose fibers present in this coating leads to high mechanical stability and energy dissipation with minimal cellulose concentration. The conformal, biocompatible, and lubricious nature of the in situ grown cellulose surfaces makes the coated 3D objects attractive for biomedical applications.

Development and thorough characterization of the processing steps of an ink for 3D printing for bone tissue engineering.

Achieving reproducibility in the 3D printing of biomaterials requires a robust polymer synthesis method to reduce batch-to-batch variation as well as methods to assure a thorough characterization throughout the manufacturing process. Particularly biomaterial inks containing large solid fractions such as ceramic particles, often required for bone tissue engineering applications, are prone to inhomogeneity originating from inadequate mixing or particle aggregation which can lead to inconsistent printing results. The production of such an ink for bone tissue engineering consisting of gellan gum methacrylate (GG-MA), hyaluronic acid methacrylate and hydroxyapatite (HAp) particles was therefore optimized in terms of GG-MA synthesis and ink preparation process, and the ink's printability was thoroughly characterized to assure homogeneous and reproducible printing results. A new buffer mediated synthesis method for GG-MA resulted in consistent degrees of substitution which allowed the creation of large 5 g batches. We found that both the new synthesis as well as cryomilling of the polymer components of the ink resulted in a decrease in viscosity from 113 kPa·s to 11.3 kPa·s at a shear rate of 0.1 s-1 but increased ink homogeneity. The ink homogeneity was assessed through thermogravimetric analysis and a newly developed extrusion force measurement setup. The ink displayed strong inter-layer adhesion between two printed ink layers as well as between a layer of ink with and a layer without HAp. The large polymer batch production along with the characterization of the ink during the manufacturing process allows ink production in the gram scale and could be used in applications such as the printing of osteochondral grafts.

Hierarchically roughened microplatelets enhance the strength and ductility of nacre-inspired composites.

Rough interfaces featuring nanoscale asperities are known to play a major role in the mechanics of nacre. Transferring this concept to artificial bioinspired composites requires a detailed understanding about the effect of the surface topography of reinforcing elements on the mechanical performance of such materials. To gain further insights into the effect of asperity size, hierarchy and coverage on the mechanics of nacre-inspired composites, we decorate alumina microplatelets with silica nanoparticles of selected sizes and use the resulting roughened platelets as reinforcing elements (15vol%) in a commercial epoxy matrix. For a single layer of silica nanoparticles on the platelet surface, increased ultimate strain and toughness are obtained with a large roughening particle size of 250nm. On the contrary, strength and stiffness are enhanced by decreasing the size of asperities using 22nm silica particles. By combining particles of two different sizes (100nm and 22nm) in a hierarchical fashion, we are able to improve stiffness and strength of platelet-reinforced polymers while maintaining high ultimate strain and toughness. Our results indicate that carefully designed hierarchically roughened interfaces lead to a more homogeneous stress distribution within the polymer matrix between the stiff reinforcing elements. By enabling the deformation of a larger fraction of the polymer matrix, this design concept improves the mechanical response of bioinspired composites and can possibly also be exploited to enhance the performance of conventional fiber-reinforced polymers.