Additive manufacturing of highly entangled polymer networks.

Incorporation of polymer chain entanglements within a single network can synergistically improve stiffness and toughness, yet attaining such dense entanglements through vat photopolymerization additive manufacturing [e.g., digital light processing (DLP)] remains elusive.

Results of an interlaboratory study on the working curve in vat photopolymerization.

The working curve informs resin properties and print parameters for stereolithography, digital light processing, and other photopolymer additive manufacturing (PAM) technologies. First demonstrated in 1992, the working curve measurement of cure depth vs radiant exposure of light is now a foundational measurement in the field of PAM. Despite its widespread use in industry and academia, there is no formal method or procedure for performing the working curve measurement, raising questions about the utility of reported working curve parameters.

Influence of fluorescent dopants on the vat photopolymerization of acrylate-based plastic scintillators for application in neutron/gamma pulse shape discrimination.

Plastic scintillators, a class of solid-state materials used for radiation detection, were additively manufactured with vat photopolymerization. The photopolymer resins consisted of a primary dopant and a secondary dopant dissolved in a bisphenol A ethoxylate diacrylate-based matrix. The absorptive dopants significantly influence important print parameters, for example, secondary dopants decrease the light penetration depth by a factor > 12 ×.

A Data-Driven Approach to Complex Voxel Predictions in Grayscale Digital Light Processing Additive Manufacturing Using U-Nets and Generative Adversarial Networks.

Data-driven U-net machine learning (ML) models, including the pix2pix conditional generative adversarial network (cGAN), are shown to predict 3D printed voxel geometry in digital light processing (DLP) additive manufacturing. A confocal microscopy-based workflow allows for the high-throughput acquisition of data on thousands of voxel interactions arising from randomly gray-scaled digital photomasks. Validation between prints and predictions shows accurate predictions with sub-pixel scale resolution.

Synergistic Fire Resistance of Nanobrick Wall Coated 3D Printed Photopolymer Lattices.

Photopolymer additive manufacturing has become the subject of widespread interest in recent years due to its capacity to enable fabrication of difficult geometries that are impossible to build with traditional manufacturing methods. The flammability of photopolymer resin materials and the lattice structures enabled by 3D printing is a barrier to widespread adoption that has not yet been adequately addressed. Here, a water-based nanobrick wall coating is deposited on 3D printed parts with simple (i.

Characterizing light engine uniformity and its influence on liquid crystal display based vat photopolymerization printing.

Vat photopolymerization (VP) is a rapidly growing category of additive manufacturing. As VP methods mature the expectation is that the quality of printed parts will be highly reproducible. At present, detailed characterization of the light engines used in liquid crystal display (LCD)-based VP systems is lacking and so it is unclear if they are built to sufficiently tight tolerances to meet the current and/or future needs of additive manufacturing.

A 3D printed mimetic composite for the treatment of growth plate injuries in a rabbit model.

Growth plate injuries affecting the pediatric population may cause unwanted bony repair tissue that leads to abnormal bone elongation. Clinical treatment involves bony bar resection and implantation of an interpositional material, but success is limited and the bony bar often reforms. No treatment attempts to regenerate the growth plate cartilage.

Electrostatically-blind quantitative piezoresponse force microscopy free of distributed-force artifacts.

The presence of electrostatic forces and associated artifacts complicates the interpretation of piezoresponse force microscopy (PFM) and electrochemical strain microscopy (ESM). Eliminating these artifacts provides an opportunity for precisely mapping domain wall structures and dynamics, accurately quantifying local piezoelectric coupling coefficients, and reliably investigating hysteretic processes at the single nanometer scale to determine properties and mechanisms which underly important applications including computing, batteries and biology. Here we exploit the existence of an electrostatic blind spot (ESBS) along the length of the cantilever, due to the distributed nature of the electrostatic force, which can be universally used to separate unwanted long range electrostatic contributions from short range electromechanical responses of interest.

Microscale Photopatterning of Through-thickness Modulus in a Monolithic and Functionally Graded 3D Printed Part.

3D printing is transforming traditional processing methods for applications ranging from tissue engineering to optics. To fulfill its maximum potential, 3D printing requires a robust technique for producing structures with precise three-dimensional (x, y and z) control of mechanical properties. Previous efforts to realize such spatial control of modulus within 3D printed parts have largely focused on low-resolution (mm to cm scale) multi-material processes and grayscale approaches that spatially vary the modulus in the x-y plane and energy dose-based ( = ) models that do not account for the resin's sub-linear response to irradiation intensity.

Digital light processing in a hybrid atomic force microscope: , nanoscale characterization of the printing process.

Stereolithography (SLA) and digital light processing (DLP) are powerful additive manufacturing techniques that address a wide range of applications including regenerative medicine, prototyping, and manufacturing. Unfortunately, these printing processes introduce micrometer-scale anisotropic inhomogeneities due to the resin absorptivity, diffusivity, reaction kinetics, and swelling during the requisite photoexposure. Previously, it has not been possible to characterize high-resolution mechanical heterogeneity as it develops during the printing process.

Permanent and reversibly programmable shapes in liquid crystal elastomer microparticles capable of shape switching.

Reversibly programmable liquid crystal elastomer microparticles (LCEMPs), formed as a covalent adaptable network (CAN), with an average diameter of 7 μm ± 2 μm, were synthesized via a thiol-Michael dispersion polymerization. The particles were programmed to a prolate shape via a photoinitiated addition-fragmentation chain-transfer (AFT) exchange reaction by activating the AFT after undergoing compression. Due to the thermotropic nature of the AFT-LCEMPs, shape switching was driven by heating the particles above their nematic-isotropic phase transition temperature (T).

Snakeskin-Inspired Elastomers with Extremely Low Coefficient of Friction under Dry Conditions.

Soft elastomers are critical to a broad range of existing and emerging technologies. One major limitation of soft elastomers is the large friction of coefficient (COF) due to inherently large adhesion and internal loss. In applications where lubrication is not applicable, such as soft robotics, wearable electronics, and biomedical devices, elastomers with inherently low dry COF are required.

Defining the Cardiac Fibroblast Secretome in a Fibrotic Microenvironment.

Background Cardiac fibroblasts (CFs) have the ability to sense stiffness changes and respond to biochemical cues to modulate their states as either quiescent or activated myofibroblasts. Given the potential for secretion of bioactive molecules to modulate the cardiac microenvironment, we sought to determine how the CF secretome changes with matrix stiffness and biochemical cues and how this affects cardiac myocytes via paracrine signaling. Methods and Results Myofibroblast activation was modulated in vitro by combining stiffness cues with TGFβ1 (transforming growth factor β 1) treatment using engineered poly (ethylene glycol) hydrogels, and in vivo with isoproterenol treatment.

Photo-tunable hydrogel mechanical heterogeneity informed by predictive transport kinetics model.

Understanding the three-dimensional (3D) mechanical and chemical properties of distinctly different, adjacent biological tissues is crucial to mimicking their complex properties with materials. 3D printing is a technique often employed to spatially control the distribution of the biomaterials, such as hydrogels, of interest, but it is difficult to print both mechanically robust (high modulus and toughness) and biocompatible (low modulus) hydrogels in a single structure. Moreover, due to the fast diffusion of mobile species during printing and nonequilibrium swelling conditions of low-solids-content hydrogels, it is challenging to form the high-fidelity structures required to mimic tissues.

Obtaining diffraction patterns from annular dark-field STEM-in-SEM images: Towards a better understanding of image contrast.

This contribution demonstrates experimentally how a series of annular dark-field transmission images collected in a scanning electron microscope (SEM) with a basic solid-state detector can be used to quantify electron scattering distributions (i.e., diffraction patterns).

Controlled Growth of Polyamide Films atop Homogenous and Heterogeneous Hydrogels using Gel-Liquid Interfacial Polymerization.

Controlled growth of crosslinked polyamide (PA) thin films is demonstrated at the interface of a monomer-soaked hydrogel and an organic solution of the complementary monomer. Termed gel-liquid interfacial polymerization (GLIP), the resulting PA films are measured to be chemically and mechanically analogous to the active layer in thin film composite membranes. PA thin films are prepared using the GLIP process on both a morphologically homogeneous hydrogel prepared from poly(2-hydroxyethylmethacrylate) (PHEMA) and a phase-separated, heterogeneous hydrogel prepared from poly(acrylamide) (PAAm).

Monitoring Fast, Voxel-Scale Cure Kinetics via Sample-Coupled-Resonance Photorheology.

Photopolymerizable materials are the focus of extensive research across a variety of fields ranging from additive manufacturing to regenerative medicine. However, poorly understood material mechanical and rheological properties during polymerization at the relevant exposure powers and single-voxel length-scales limit advancements in part performance and throughput. Here, a novel atomic force microscopy (AFM) technique, sample-coupled-resonance photorheology (SCRPR), to locally characterize the mechano-rheological properties of photopolymerized materials on the relevant reaction kinetic timescales, is demonstrated.

Nanomechanics of cellulose deformation reveal molecular defects that facilitate natural deconstruction.

Technologies surrounding utilization of cellulosic materials have been integral to human society for millennia. In many materials, controlled introduction of defects provides a means to tailor properties, introduce reactivity, and modulate functionality for various applications. The importance of defects in defining the behavior of cellulose is becoming increasingly recognized.

Decoupling subsurface inhomogeneities: a 3D finite element approach for contact nanomechanical measurements.

Novel material properties can be attained when embedding three-dimensional (3D) nanoparticles (NPs) in a variety of polymeric matrices. These inhomogeneities influence the bulk mechanical response due to the local high modulus mismatch between the particles and the matrix. The degree of the mechanical mismatch that is seen near a composite surface depends on the geometry/shape and spatial location and orientation of the particle with respect to the external contact loading.

A readily programmable, fully reversible shape-switching material.

Liquid crystalline (LC) elastomers (LCEs) enable large-scale reversible shape changes in polymeric materials; however, they require intensive, irreversible programming approaches in order to facilitate controllable actuation. We have implemented photoinduced dynamic covalent chemistry (DCC) that chemically anneals the LCE toward an applied equilibrium only when and where the light-activated DCC is on. By using light as the stimulus that enables programming, the dynamic bond exchange is orthogonal to LC phase behavior, enabling the LCE to be annealed in any LC phase or in the isotropic phase with various manifestations of this capability explored here.

Scanning speed phenomenon in contact-resonance atomic force microscopy.

This work presents data confirming the existence of a scan speed related phenomenon in contact-mode atomic force microscopy (AFM). Specifically, contact-resonance spectroscopy is used to interrogate this phenomenon. Above a critical scan speed, a monotonic decrease in the recorded contact-resonance frequency is observed with increasing scan speed.

Influence of support-layer deformation on the intrinsic resistance of thin film composite membranes.

It is commonly believed that the overall permeation resistance of thin film composite (TFC) membranes is dictated by the crosslinked, ultrathin polyamide barrier layer, while the porous support merely serves as the mechanical support. Although this assumption might be the case under low transmembrane pressure, it becomes questionable under high transmembrane pressure. A highly porous support normally yields under a pressure of a few MPa, which can result in a significant level of compressive strain that may significantly increase the resistance to permeation.

Determination of the True Lateral Grain Size in Organic-Inorganic Halide Perovskite Thin Films.

In this letter, methylammonium lead iodide (MAPbI) thin films were examined via piezoresponse force microscopy (PFM) and nanoindentation (NI) to determine if long-range atomic order existed across the full width and depth of the apparent grains. From the PFM, the piezoelectric response of the films was strongly correlated with low-index planes of the crystal structure and ferroelastic domains in macroscale solution-grown MAPbI crystals, which implied long-range order near the top surface. From the NI, it was found that the induced cracks were straight and extended across the full width of the apparent grains, which indicated that the long-range order was not limited to the near-surface region, but extended through the film thickness.