real-time-imaging-of-bonding-in-3d-printed-layers

Real-Time Imaging of Bonding in 3D-Printed Layers

In recent times, 3D printing technology has revolutionized our ability to design and produce products, but optimizing the print quality can be ...

Confocal microscopy is widely used for three-dimensional (3D) sample reconstructions. Arguably, the most significant challenge in such reconstructions is posed by the resolution along the optical axis being significantly lower than in the lateral directions. In addition, the imaging rate is lower along the optical axis in most confocal architectures, prohibiting reliable 3D reconstruction of dynamic samples. Here, we demonstrate a very simple, cheap, and generic method of multiangle microscopy, allowing high-resolution high-rate confocal slice collection to be carried out with capillary-contained colloidal samples in a wide range of slice orientations. This method, realizable with any common confocal architecture and recently implemented with macroscopic specimens enclosed in rotatable cylindrical capillaries, allows 3D reconstructions of colloidal structures to be verified by direct experiments and provides a solid testing ground for complex reconstruction algorithms. In this paper, we focus on the implementation of this method for dense nonrotatable colloidal samples, contained in complex-shaped capillaries. Additionally, we discuss strategies to minimize potential pitfalls of this method, such as the artificial appearance of chain-like particle structures.

Axial Confocal Tomography of Capillary-Contained Colloidal Structures.

The assembly of semiconductor nanoparticles, quantum dots (QDs), into dense crystalline nanostructures holds great promise for future optoelectronic devices. However, knowledge of the sub-nanometer scale driving forces underlying the kinetic processes of nucleation, growth, and final densification during QD assembly remains poor. Emulsion-templated assembly has recently been shown to provide good control over the bulk condensation of QDs into highly ordered 3D supercrystals. Here, emulsion-templated assembly is combined with in situ small-angle X-ray scattering to obtain direct insight into the nanoscale interactions underlying the nucleation, growth, and densification of QD supercrystals. At the point of supercrystal nucleation, nanoparticles undergo a hard-sphere-like crystallization into a hexagonal-close-packed lattice, slowly transforming into a face-centered-cubic lattice. The ligands play a crucial role in balancing steric repulsion against attractive van der Waals forces to mediate the initial equilibrium assembly, but cause the QDs to be progressively destabilized upon densification. The rich detail of this kinetic study elucidates the assembly and thermodynamic properties that define QD supercrystal fabrication approaching single-crystal quality, paving the way toward their use in optoelectronic devices.

Revealing Driving Forces in Quantum Dot Supercrystal Assembly.

Sufficiently strong interparticle attractions can lead to aggregation of a colloidal suspension and, at high enough volume fractions, form a mechanically rigid percolating network known as a colloidal gel. We synthesize a model thermo-responsive colloidal system for systematically studying the effect of surface properties, grafting density and chain length, on the particle dynamics within colloidal gels. After inducing an attraction between particles by heating, aggregates undergo thermal fluctuation which we observe and analyze microscopically; the magnitude of the variance in bond angle is larger for lower grafting densities. Macroscopically, a clear increase of the linear mechanical behavior of the gels on both the grafting density and chain length arises, as measured by rheology, which is inversely proportional to the magnitude of local bond angle fluctuations. This colloidal system will allow for further elucidation of the microscopic origins to the complex macroscopic mechanical behavior of colloidal gels including bending modes within the network.

Temperature-Triggered Colloidal Gelation through Well-Defined Grafted Polymeric Surfaces.

The assembly of colloidal quantum dots (QDs) into dense superstructures holds great promise for the development of novel optoelectronic devices. Several assembly techniques have been explored; however, achieving direct and precise control over the interparticle potential that controls the assembly has proven to be challenging. Here, we exploit the application of critical Casimir forces to drive the growth of QDs into superstructures. We show that the exquisite temperature-dependence of the critical Casimir potential offers new opportunities to control the assembly process and morphology of the resulting QD superstructures. The direct assembly control allows us to elucidate the relation between structural, optical, and conductive properties of the critical Casimir-grown QD superstructures. We find that the choice of the temperature setting the interparticle potential plays a central role in maximizing charge percolation across QD thin-films. These results open up new directions for controlling the assembly of nanostructures and their optoelectronic properties.

Controlling Superstructure-Property Relationships via Critical Casimir Assembly of Quantum Dots.

Low-fat food products often contain natural, edible polymers to retain the desired mouth feel and elasticity of their full-fat counterparts. This type of product, however, can suffer from syneresis: densification due to the expulsion of fluid. Gaining insight into the physical principles governing syneresis in such soft hybrid dispersions remains a challenge from a theoretical perspective, as experimental data are needed to establish a basis. We record non-accelerated syneresis in a model system for low-fat mayonnaise: a colloid polymer mixture, consisting of oil in water emulsion with starch in the aqueous phase. We find the flow rate of expelled fluid to be proportional to the difference in hydrostatic pressure over the system. The osmotic pressure of the added starch, while being higher than the hydrostatic pressure, does not prevent syneresis because the soluble starch is lost to the expelled fluid. From these findings, we conclude that forced syneresis in these systems can be described as a gravity-driven porous flow through the densely packed emulsion, explainable with a model based on Darcy's law.

Gravity-driven syneresis in model low-fat mayonnaise.

Underwater adhesion represents a huge technological challenge as the presence of water compromises the performance of most commercially available adhesives. Inspired by natural organisms, we have designed an adhesive based on complex coacervation, a liquid-liquid phase separation phenomenon. A complex coacervate adhesive is formed by mixing oppositely charged polyelectrolytes bearing pendant thermoresponsive poly(-isopropylacrylamide) (PNIPAM) chains. The material fully sets underwater due to a change in the environmental conditions, namely temperature and ionic strength. In this work, we incorporate silica nanoparticles forming a hybrid complex coacervate and investigate the resulting mechanical properties. An enhancement of the mechanical properties is observed below the PNIPAM lower critical solution temperature (LCST): this is due to the formation of PNIPAM-silica junctions, which, after setting, contribute to a moderate increase in the moduli and in the adhesive properties only when applying an ionic strength gradient. By contrast, when raising the temperature above the LCST, the mechanical properties are dominated by the association of PNIPAM chains and the nanofiller incorporation leads to an increased heterogeneity with the formation of fracture planes at the interface between areas of different concentrations of nanoparticles, promoting earlier failure of the network-an unexpected and noteworthy consequence of this hybrid system.

Hybrid Complex Coacervate.

Inorganic perovskites display an enticing foreground for their wide range of optoelectronic applications. Recently, supercrystals (SCs) of inorganic perovskite nanocrystals (NCs) have been reported to possess highly ordered structure as well as novel collective optical properties, opening new opportunities for efficient films. Here, we report the large-scale assembly control of spherical, cubic, and hexagonal SCs of inorganic perovskite NCs through templating by oil-in-oil emulsions. We show that an interplay between the roundness of the cubic NCs and the tension of the confining droplet surface sets the superstructure morphology, and we exploit this interplay to design dense hyperlattices of SCs. The SC films show strongly enhanced stability for at least two months without obvious structural degradation and minor optical changes. Our results on the controlled large-scale assembly of perovskite NC superstructures provide new prospects for the bottom-up production of optoelectronic devices based on the microfluidic production of mesoscopic building blocks.

Highly Stable Perovskite Supercrystals via Oil-in-Oil Templating.

Nonadsorbing polymers are widely used as thickening agents for colloids. A quantitative description of the structure and dynamics of such colloid-polymer mixtures is crucial to reveal the mechanisms accounting for the desired mechanical properties. We use confocal microscopy to study colloids with three types of commonly used polymers with different architectures: linear, subgranular cross-linked, and branched microgels. All three thickeners give rise to heterogeneous colloidal dynamics, characterized by non-Gaussian displacement distributions. However, while the ensemble-averaged particle dynamics in these materials are very similar, the underlying individual particle dynamics are not. Linear polymers give rise to depletion attraction and the formation of colloidal gels, in which the majority of particles are immobilized, while a few weakly bound particles have much higher mobility. By contrast, the branched and cross-linked polymers thicken the continuous phase of the colloid, squeezing the particles into dense pockets, where the mobility is reduced and requires more cooperative rearrangements.

Particle Dynamics in Colloid-Polymer Mixtures with Different Polymer Architectures.

Semiconductor nanocrystals, or quantum dots (QDs), simultaneously benefit from inexpensive low-temperature solution processing and exciting photophysics, making them the ideal candidates for next-generation solar cells and photodetectors. While the working principles of these devices rely on light absorption, QDs intrinsically belong to the Rayleigh regime and display optical behavior limited to electric dipole resonances, resulting in low absorption efficiencies. Increasing the absorption efficiency of QDs, together with their electronic and excitonic coupling to enhance charge carrier mobility, is therefore of critical importance to enable practical applications. Here, we demonstrate a general and scalable approach to increase both light absorption and excitonic coupling of QDs by fabricating hierarchical metamaterials. We assemble QDs into crystalline supraparticles using an emulsion template and demonstrate that these colloidal supercrystals (SCs) exhibit extended resonant optical behavior resulting in an enhancement in absorption efficiency in the visible range of more than 2 orders of magnitude with respect to the case of dispersed QDs. This successful light trapping strategy is complemented by the enhanced excitonic coupling observed in ligand-exchanged SCs, experimentally demonstrated through ultrafast transient absorption spectroscopy and leading to the formation of a free biexciton system on sub-picosecond time scales. These results introduce a colloidal metamaterial designed by self-assembly from the bottom up, simultaneously featuring a combination of nanoscale and mesoscale properties leading to simultaneous photonic and excitonic coupling, therefore presenting the nanocrystal analogue of supramolecular structures.

Simultaneous Photonic and Excitonic Coupling in Spherical Quantum Dot Supercrystals.

Linear-bottlebrush-linear (LBBL) triblock copolymers are emerging systems for topologically-tunable elastic materials. In this paper, a new synthetic methodology is presented to synthesize LBBL polystyrene--bottlebrushpolydimethylsiloxane--polystyrene (PS--bbPDMS--PS) triblock copolymer  the "grafting onto" approach where the precursors are individually synthesized through living anionic polymerization and selective coupling reaction. In this two-step approach, polystyrene--polymethylvinylsiloxane (PS--PMVS) diblock copolymer with a low dispersity couples with another living PS block to form PS--PMVS--PS triblock copolymer. Secondly, this is followed by grafting of separately prepared monohydride-terminated PDMS chains with controllable grafting density through a hydrosilylation reaction. In addition to fully tunable architectural parameters, this approach permits a quantitative determination of the ratio of diblock and triblock bottlebrush copolymers and consistency between batches, highlighting the feasibility for scaled-up production. These LBBL triblock copolymers self-assemble into soft, low-modulus thermoplastic elastomers, and the precise knowledge of the composition is crucial for correlating microstructure to mechanical properties.

Synthesis of well-defined linear-bottlebrush-linear triblock copolymer towards architecturally-tunable soft materials.

The drying of a multi-component dispersion, such as water-based paint, ink and sunscreen to form a solid film, is a widespread process. Binary colloidal suspensions have proven capable of spontaneous layer formation through size segregation during drying. To design bespoke stratification patterns, a deeper understanding of how these emerge is crucial. Here, we visualize and quantify the spatiotemporally evolving concentration profiles in situ and with high resolution using confocal fluorescence microscopy of custom-designed binary dispersions in a well-defined geometry. Our results conclusively establish two distinct stratification routes, which give rise to three layered structures. A first thin layer develops directly underneath the evaporation front in which large particles are kinetically trapped. At later times, asymmetrical particle interactions lead to the formation of two subsequent layers enriched in small and large particles, respectively. The spatial extent and magnitude of demixing strongly depend on the initial volume fraction. We explain and reproduce the experimental concentration profiles using a theoretical model based on dynamic arrest and higher-order thermodynamic and hydrodynamic interactions. These insights unravel the key mechanisms underlying colloidal auto-stratification in multi-component suspensions, and allow preprogramming of stratification patterns in single-deposition formulations for future applications.

In-situ and quantitative imaging of evaporation-induced stratification in binary suspensions.

Syneresis, the compaction of a material accompanied by fluid expulsion, is a typical mechanical instability which exists among colloidal gel based materials and that negatively affects the quality of relevant applications. We shed light onto the internal dynamics of model colloidal gels undergoing syneresis using Laser Speckle Imaging (LSI). The resulting dynamical maps capture the distinct differences in spatial and temporal relaxation patterns between colloidal gels comprising solid and liquid particles. This indicates different mechanisms of syneresis between the two systems and highlights the importance of the constituent particles and their mobile or restrictive interfaces in the mechanical relaxation of the colloidal gels during syneresis.

Spatially heterogenous dynamics in colloidal gels during syneresis.

We assemble semiconductor CdSe nanoplatelets (NPs) at the air/liquid interface into 2D monolayers several micrometers wide, distinctly displaying nematic order. We show that this configuration is the most favorable energetically and that the edge-to-edge distance between neighboring NPs can be tuned by ligand exchange without disrupting film topology and nanoparticle orientation. We explore the rich assembly phase space by using depletion interactions to direct the formation of 1D nanowires from stacks of NPs. The improved control and understanding of the assembly of semiconductor NPs offers opportunities for the development of cheaper optoelectronic devices that rely on 1D or 2D charge delocalization throughout the assembled monolayers and nanowires.

Article	Year
Axial Confocal Tomography of Capillary-Contained Colloidal Structures. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 29043816	2017
Revealing Driving Forces in Quantum Dot Supercrystal Assembly. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 30133015	2018
Temperature-Triggered Colloidal Gelation through Well-Defined Grafted Polymeric Surfaces. Gels (Basel, Switzerland)\| PubMed ID: 30920518	2017
Controlling Superstructure-Property Relationships via Critical Casimir Assembly of Quantum Dots. The journal of physical chemistry. C, Nanomaterials and interfaces\| PubMed ID: 31205576	2019
Gravity-driven syneresis in model low-fat mayonnaise. Soft matter\| PubMed ID: 31696190	2019
Hybrid Complex Coacervate. Polymers\| PubMed ID: 32033133	2020
Highly Stable Perovskite Supercrystals via Oil-in-Oil Templating. Nano letters\| PubMed ID: 32701303	2020
Particle Dynamics in Colloid-Polymer Mixtures with Different Polymer Architectures. ACS applied materials & interfaces\| PubMed ID: 32812728	2020
Simultaneous Photonic and Excitonic Coupling in Spherical Quantum Dot Supercrystals. ACS nano\| PubMed ID: 32924433	2020
Synthesis of well-defined linear-bottlebrush-linear triblock copolymer towards architecturally-tunable soft materials. Polymer chemistry\| PubMed ID: 36092984	2022
In-situ and quantitative imaging of evaporation-induced stratification in binary suspensions. Journal of colloid and interface science\| PubMed ID: 36347093	2023
Spatially heterogenous dynamics in colloidal gels during syneresis. Soft matter\| PubMed ID: 37403813	2023
Controlled Assembly of CdSe Nanoplatelet Thin Films and Nanowires. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 37561597	2023

Thomas E. Kodger

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