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At least 127 records · Page 7

3D printable silicone compositions exhibiting high toughness and low durometer

3D printable silicones can be designed with varying crosslink density, network structures, and types of reinforcing additives. Within this design space, one may tailor the uncured material’s rheology and mechanical response to access a wide range of potential applications. However, printable, low modulus silicones, particularly those applicable to direct ink write, are underreported in published literature. To address the need for higher performance, low modulus silicones with demonstrated printability, a new set of ca. 20–50 Shore A hardness silicone elastomers exhibiting ca. 7 MPa ultimate tensile strength and ca. 400–1200% elongation at break is presented. Mechanical properties were analyzed, providing insight to the effects of formulation constituents on mechanical properties. Cyclic mechanical testing of the silicone formulations was also performed, and the energy loss and permanent set throughout cycling were determined. In conclusion, printed structures demonstrate the feasibility of these new silicones as durable frameworks for novel soft device applications.

36 MATERIALS SCIENCE↗

Spectroscopic Investigation of Catalyst Inks and Thin Films Toward the Development of Ionomer Quality Control

As the production of polymer electrolyte fuel cells expands, novel quality control methods must be invented or adapted in order to support expected rates of production. Ensuring the quality of deposited catalyst layers is an essential step in the fuel cell manufacturing process, as the efficiency of a fuel cell is reliant on the catalyst layer being uniform at both the target platinum loading and the target ionomer content. Implementing a quality control method that is sensitive to these aspects is imperative, as wasting precious metals and other catalyst materials is expensive, and represents a potential barrier to entry into the field for manufacturers experimenting with novel deposition processes. In this work, we analyzed catalyst inks to determine if their ionomer content could be quantized spectroscopically. Attenuated total reflection (ATR) Fourier transform infrared spectroscopic technique was investigated producing a signal proportional to the ionomer content. ATR spectroscopy was able to quantitatively differentiate samples in which the ionomer to carbon mass ratio (I/C) varied between 0.9 and 3.0. The I/C ratio was correlated to the measured ATR signal near the CF 2 vibrational bands located between 1100 cm −1 and 1400 cm −1 . The experimental results obtained constitute a step toward the development of novel quality control methodologies for catalyst inks utilized by the fuel cell industry.

30 DIRECT ENERGY CONVERSION↗

Poly(lactic acid)-Based Ink for Biodegradable Printed Electronics With Conductivity Enhanced through Solvent Aging

Biodegradable electronics is a rapidly growing field, and the development of controllably biodegradable, high-conductivity materials suitable for additive manufacturing under ambient conditions remains a challenge. Here, printable conductive pastes that employ poly(lactic acid) (PLA) as a binder and tungsten as a conductor are demonstrated. These composite conductors can provide enhanced stability in applications where moisture may be present, such as environmental monitoring or agriculture. Post-processing the printed traces using a solvent-aging technique increases their conductivity by up to 2 orders of magnitude, with final conductivities approaching 5000 S/m. Such techniques could prove useful when thermal processes including heating or laser sintering are limited by the temperature constraints of typical biodegradable substrates. Finally, both accelerated oxidative and hydrolytic degradation of the printed composite conductors are examined, and a fully biodegradable capacitive soil moisture sensor is fabricated and tested.

36 MATERIALS SCIENCE↗

The Impact of Catalyst Layer Properties and Transport Layer Interactions on Rutile Iridium Oxide Anode Durability in Proton Exchange Membrane Electrolysis

The performance and durability of proton exchange membrane electrolyzers are governed by the interplay between catalyst inks and integration, the resulting catalyst layer (CL) structure, and the interface between the CL and porous transport layer (PTL). In this study, we examine the impact of these factors on cell performance and degradation using rutile IrO2 as the anode catalyst. The two commercial rutile IrO2 catalysts differ from each other and from the amorphous benchmark in agglomerate size and ink stability. This has implications for CL morphology and electronic connectivity. In the context of long-term pressurized operation for up to 1000 h, the selection of the PTL has a marginal effect on the durability of CLs with good structural and compositional properties, whereas poorly structured CLs demonstrate evident degradation when used with certain PTLs. Poor CL properties amplify the negative impact of non-ideal CL/PTL interfaces, demonstrating the importance of CL/PTL interface engineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid custom prototyping of soft poroelastic biosensor for simultaneous epicardial recording and imaging

Abstract The growing need for the implementation of stretchable biosensors in the body has driven rapid prototyping schemes through the direct ink writing of multidimensional functional architectures. Recent approaches employ biocompatible inks that are dispensable through an automated nozzle injection system. However, their application in medical practices remains challenged in reliable recording due to their viscoelastic nature that yields mechanical and electrical hysteresis under periodic large strains. Herein, we report sponge-like poroelastic silicone composites adaptable for high-precision direct writing of custom-designed stretchable biosensors, which are soft and insensitive to strains. Their unique structural properties yield a robust coupling to living tissues, enabling high-fidelity recording of spatiotemporal electrophysiological activity and real-time ultrasound imaging for visual feedback. In vivo evaluations of custom-fit biosensors in a murine acute myocardial infarction model demonstrate a potential clinical utility in the simultaneous intraoperative recording and imaging on the epicardium, which may guide definitive surgical treatments.

36 MATERIALS SCIENCE↗

Additive manufacturing of nanotube-loaded thermosets via direct ink writing and radio-frequency heating and curing

Direct Ink Writing (DIW) is an extrusion-based additive manufacturing method where the print medium is a liquid-phase ‘ink’ dispensed out of nozzles and deposited along digitally defined paths. Conventional DIW of thermosetting resins relies on viscosity modifying agents, novel crosslinking chemistries, and/or long curing schedules in an oven. Here we demonstrate the use of a co-planar radio frequency applicator to generate an electric field, which can be used to rapidly heat and cure nano-filled composite resins as they are printed. This method avoids the need for an oven or post- curing step. This process consists of a sequential print-and-cure cycle which allows for printing of high-resolution, multi-layered structures. Every extruded layer is partially cured using RF before depositing the next layer; this allows the printed part to maintain structural integrity. The process enables both increased throughput and decreased touch time relative to traditional manufacturing. Commercial epoxy resin with varied nano-filler loadings were examined as DIW candidates. After printing, the thermo-mechanical properties, surface finish, and shape retention of RF-cured samples were comparable to conventionally cured samples. Furthermore, this method of manufacturing establishes RF heating as a suitable alternative to conventional methods, facilitating rapid, free-form processing of thermosetting resins without a mold.

36 MATERIALS SCIENCE↗

Dielectric Barrier Discharge Electrothermal Heating and Additive Manufacturing of Thermoset Parts

Additive manufacturing of thermosets requires a mechanism for solidifying deposited layers in order to prevent part collapse. To accomplish this, non‐equilibrium plasma is proposed for its ability to target, heat, and cure printed thermosetting resin. Non‐equilibrium plasmas have not been used for the curing of liquid thermoset composites, and so their impact on an uncured resin is unknown. Here this work investigates the mechanism through which dielectric barrier discharge (DBD) heats an epoxy/carbon nanotube (CNT) composite under atmospheric conditions. Plasma applied to resin surfaces is found to cause rapid heating, with heating rate controlled by adjusting the applied power. Heating is localized to within the top 0.5 mm of the sample surface and maximum temperature is found to depend on sample conductivity, indicating the heating reaction occurs through a combination of electron conduction and ion bombardment. Characterization of composites cured using plasma shows oxidation and roughening of the surface. Based on the heating and surface studies, several demonstrative prints are performed using in situ plasma curing. This work shows the potential of DBD plasma to rapidly heat liquid substrates and demonstrates how plasma curing expands the capability of existing direct ink write (DIW) printer technologies.

3D printing↗

Direct Ink-Write Printing of Ceramic Clay with an Embedded Wireless Temperature and Relative Humidity Sensor

This research presents a simple method to additively manufacture Cone 5 porcelain clay ceramics by using the direct ink-write (DIW) printing technique. DIW has allowed the application of extruding highly viscous ceramic materials with relatively high-quality and good mechanical properties, which additionally allows a freedom of design and the capability of manufacturing complex geometrical shapes. Clay particles were mixed with deionized (DI) water at different ratios, where the most suitable composition for 3D printing was observed at a 1:5 w/c ratio (16.2 wt.%. of DI water). Differential geometrical designs were printed to demonstrate the printing capabilities of the paste. In addition, a clay structure was fabricated with an embedded wireless temperature and relative humidity (RH) sensor during the 3D printing process. The embedded sensor read up to 65% RH and temperatures of up to 85 °F from a maximum distance of 141.7 m. The structural integrity of the selected 3D printed geometries was confirmed through the compressive strength of fired and non-fired clay samples, with strengths of 70 MPa and 90 MPa, respectively. This research demonstrates the feasibility of using the DIW printing of porcelain clay with embedded sensors, with fully functional temperature- and humidity-sensing capabilities.

42 ENGINEERING↗

Using scalable computer vision to automate high-throughput semiconductor characterization

Abstract High-throughput materials synthesis methods, crucial for discovering novel functional materials, face a bottleneck in property characterization. These high-throughput synthesis tools produce 10 4 samples per hour using ink-based deposition while most characterization methods are either slow (conventional rates of 10 1 samples per hour) or rigid (e.g., designed for standard thin films), resulting in a bottleneck. To address this, we propose automated characterization (autocharacterization) tools that leverage adaptive computer vision for an 85x faster throughput compared to non-automated workflows. Our tools include a generalizable composition mapping tool and two scalable autocharacterization algorithms that: (1) autonomously compute the band gaps of 200 compositions in 6 minutes, and (2) autonomously compute the environmental stability of 200 compositions in 20 minutes, achieving 98.5% and 96.9% accuracy, respectively, when benchmarked against domain expert manual evaluation. These tools, demonstrated on the formamidinium (FA) and methylammonium (MA) mixed-cation perovskite system FA 1−x MA x PbI 3 , 0 ≤ x ≤ 1, significantly accelerate the characterization process, synchronizing it closer to the rate of high-throughput synthesis.

Science & Technology - Other Topics↗

Additive manufacturing of high explosives with inert dilution for wave shaping and detonation velocity grading

The performance of a high explosive charge is highly influenced by the detonation velocity and any inherent internal structure. Additively manufactured (AM) high explosive charges allow for a precisely engineered internal structure and the selective placement of discrete or graded volumes of a tailored material, which are unachievable by conventional means. The dilution of a solid explosive by an inert additive for detonation velocity reduction is herein evaluated for a method of material extrusion called a direct-ink-write AM, where an 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane-based ultraviolet -curable energetic-binder paste explosive was diluted by the inert density mock 5-iodo-2′-deoxyuridine for use in the manufacture of multi-material explosive charges. The explosive ink was characterized for printing by rheological and particle size measurements, and the detonation velocities for 0–40 wt. % inert diluent were found to have a continuous linear reduction in detonation velocity down to 14.3% difference. A two-component 3D plane wave explosive lens with 8.038 km/s “fast” and 7.491 km/s “slow” diluted ink in an internal cone demonstrated a reduced time of breakout at the output face from 361 to 53 ns. A linearly graded “fast–slow–fast” cylinder was successfully printed and fired, showing engineered control along the length of the charge as the detonation velocity dropped from 7.851 to 6.700 km/s and then recovered to 7.241 km/s. The extreme control over the internal composition of a high explosive charge via a dual-material extruder/mixer challenges conventional manufacturing approaches and opens new avenues for engineered detonation wavefronts, high explosive charge performance, and new applications.

36 MATERIALS SCIENCE↗

3D Printing of High Viscosity Reinforced Silicone Elastomers

Recent advances in additive manufacturing, specifically direct ink writing (DIW) and ink-jetting, have enabled the production of elastomeric silicone parts with deterministic control over the structure, shape, and mechanical properties. These new technologies offer rapid prototyping advantages and find applications in various fields, including biomedical devices, prosthetics, metamaterials, and soft robotics. Stereolithography (SLA) is a complementary approach with the ability to print with finer features and potentially higher throughput. However, all high-performance silicone elastomers are composites of polysiloxane networks reinforced with particulate filler, and consequently, silicone resins tend to have high viscosities (gel- or paste-like), which complicates or completely inhibits the layer-by-layer recoating process central to most SLA technologies. Herein, the design and build of a digital light projection SLA printer suitable for handling high-viscosity resins is demonstrated. Further, a series of UV-curable silicone resins with thiol-ene crosslinking and reinforced by a combination of fumed silica and MQ resins are also described. The resulting silicone elastomers are shown to have tunable mechanical properties, with 100–350% elongation and ultimate tensile strength from 1 to 2.5 MPa. Three-dimensional printed features of 0.4 mm were achieved, and complexity is demonstrated by octet-truss lattices that display negative stiffness.

36 MATERIALS SCIENCE↗

Use of latent metathesis polymerization systems for additive manufacturing

The invention is directed to latent metathesis-active resin compositions and additive manufacturing approaches. The latent metathesis-active compositions comprise at least one latent metathesis catalyst, at least one curable metathesis-active monomer, and optional fillers, photosensitizers, and/or a secondary monomer resin system for dual-cure. A method comprises extruding a latent metathesis-active resin from a dispensing apparatus and spatially triggering a ring-opening metathesis polymerization by directed irradiation with light or directed application of a thermal stimuli for direct-ink write printing of objects. Another method uses a latent metathesis-active resin for vat photopolymerization and stereolithographic printing of objects.

Appelhans, Leah↗

Flexible CO 2 Sensor Architecture with Selective Nitrogen Functionalities by One‐Step Laser‐Induced Conversion of Versatile Organic Ink

Abstract Nitrogen‐containing carbons (NC) are a class of sustainable materials for selective CO 2 adsorption. A versatile concept is introduced to fabricate flexible NC‐based sensor architectures for room‐temperature sensing of CO 2 in a one‐step laser conversion of primary films cast from abundant precursors. By the unidirectional energy impact in conjunction with depth‐dependent attenuation of the laser beam, a layered sensor heterostructure with a porous transducer and active sensor layer is formed. Comprehensive microscopic and spectroscopic cross‐sectional analyses confirm the preservation of the high content of imidazolic nitrogen in the sensor. The performance is optimized in terms of material morphology, chemical composition, and surface chemistry to achieve a linear relative resistive response of up to Δ R / R 0 = −14.3% (10% of CO 2 ). Thermodynamic analysis yields Δ ads H values of −35.6 and 34.1 kJ·mol −1 for H 2 O and CO 2 , respectively. The sensor is operable even in humid environments (e.g., ∆ R / R 0,RH = 80% = 0.53%) and shows good performance upon strong mechanical deformation.

flexible gas sensors↗

One-Component, Vinyl-Functional Fluorosilicone Pastes for Direct Ink Write Additive Manufacturing

In this study, one-component (“all-in-one”) fluorosilicone pastes specifically designed for application in direct ink write (DIW) additive manufacturing (AM) have been developed. They consist of vinyl-functional, methyltrifluoropropyl-containing (MeTfpS) terpolysiloxane base polymer(s), hydrosilyl-functional cross-linker(s), UV-sensitive hydrosilylation catalyst, thixotropic additive, and trimethylsilylated fumed silica filler, with other additives that are optional. Their base polymers were completely amorphous and linear, with molecular weights (M n ) ranging from approximately 7000 to 50,000 and specifically targeted for the viscosity range ideal for DIW. These polymers were prepared by anionic ring-opening polymerizations (A-ROP) of appropriate mixtures of cyclic siloxanes initiated by oligomeric, difunctional tetramethylammonium silanolate in the presence of a difunctional tetramethyldivinyldisiloxane end-blocker and molecular weight regulator. Two series of these terpolymers were prepared: one containing 5 mol % MeTfpS repeat units but varying degrees of polymerization (DP) from 80 to 600 and the other containing 5, 10, and 15 mol % MeTfpS at a constant DP of 600. All polymers contained mostly random distributions of MeTfpS repeat units. The pastes were prepared by speed-mixing, ready for use in DIW, they exhibited ideal thixotropy, long-term (over a year) rheological stability, and can be quickly (within seconds) and permanently cured by room-temperature, UV-activated hydrosilylation in air. The resulting elastomers showed base polymer molecular weight- and composition-dependent stress-induced crystallization (SIC) at higher molecular weights and lower trifluoropropyl contents and tunable Shore A hardness (30A–40A) typical for soft polysiloxane rubbers. Preliminary DIW tests indicated excellent printability with high precision of printed shapes and clearly present these one-component pastes as prime candidates for simple and practical printing of silicone elastomer objects.

36 MATERIALS SCIENCE↗

3D printed transparent ceramic YAG laser rods: Matching the core-clad refractive index

Yttrium Aluminum Garnet (YAG) solid state laser gain media rods with an active Neodymium-doped core and an optically-clear cladding region were additively manufactured via direct-ink-writing (DIW), followed by sintering and hot isostatic pressing to form fully dense optical ceramics. Lutetium and Gadolinium were chosen as optically-inert co-doping ions in the clad to match the increase in refractive index caused by the Neodymium in the core. Additionally, either 11.6% Lutetium or 3.8% Gadolinium can be used to match the index change from 2% neodymium; however, differences in diffusion distances across the core-clad interface lead to large fluctuations in index in that region. These index fluctuations can be minimized either by matching dopants with similar diffusion distances, or by implementing a gradual gradient in the doping profile, possible through DIW, rather than a sharp compositional interface attainable via more standard fabrication methods. This improvement in index homogeneity resulted in a 40% improvement in lasing performance compared with that of a core-clad rod fabricated with a sharp interface between the doped and undoped regions.

36 MATERIALS SCIENCE↗

Thermomechanical properties of stereolithographic 3D-printed zinc oxide nanocomposites

Stereolithography (SLA) is a highly versatile additive manufacturing technique that utilizes various ink formulations to fabricate 3D-printed nanocomposite structures with desired properties. Zinc oxide (ZnO) is a promising candidate due to its excellent mechanical and thermal stability, and compatibility with various polymeric matrices. Here, in this work, varying ink formulations containing ZnO nanoparticles, along with employing appropriate post-printing curing parameters to fabricate SLA 3D-printed acrylate-based nanocomposites with improved mechanical and thermal properties, were reported. This study can significantly contribute to expanding its potential use in practical applications such as biomedical and structural applications.

36 MATERIALS SCIENCE↗

Composition-Dependent Photoluminescence Properties and Anti-Counterfeiting Applications of A 2 AgX 3 (A = Rb, Cs; X = Cl, Br, I)

Copper(I) halides are emerging as attractive alternatives to lead halide perovskites for optical and electronic applications. However, blue-emitting all-inorganic copper(I) halides suffer from poor stability and lack of tunability of their photoluminescence (PL) properties. In this work, the preparation of silver(I) halides A 2 AgX 3 (A = Rb, Cs; X = Cl, Br, I) through solid-state synthesis is reported. In contrast to the Cu(I) analogs, A 2 AgX 3 are broad-band emitters sensitive to A and X site substitutions. First-principle calculations show that defect-bound excitons are responsible for the observed main PL peaks in Rb 2 AgX 3 and that self-trapped excitons (STEs) contribute to a minor PL peak in Rb 2 AgBr 3 . This is in sharp contrast to Rb 2 CuX 3 , in which the PL is dominated by the emission by STEs. Moreover, the replacement of Cu(I) with Ag(I) in A 2 AgX 3 significantly improves photostability and stability in the air under ambient conditions, which enables their consideration for practical applications. Thus, luminescent inks based on A 2 AgX 3 are prepared and successfully used in anti-counterfeiting applications. The excellent light emission properties, significantly improved stability, simple preparation method, and tunable light emission properties demonstrated by A 2 AgX 3 suggest that silver(I) halides may be attractive alternatives to toxic lead halide perovskites and unstable copper(I) halides for optical applications.

36 MATERIALS SCIENCE↗

On the 3D printability of one-part moisture-curable polyurethanes via direct ink writing (DIW)

Direct ink writing (DIW) is an ambient temperature additive manufacturing (AM) method that accommodates many possible ink materials. Here, in this work, we demonstrate using a moisture-curable commercially available polyurethane (PU) sealant as an alternative ink for DIW. We discussed the fundamentals of PU chemistry and determined the best 3D printing parameters. Studies on rheological, thermogravimetric, spectroscopic characterization, and initial finite element analyses (FEA) showed properties expected from a performance sealant with high elongation and low modulus of a 3D-printed object. This affirms the flexibility of the DIW technique as an accessible AM method amenable for future materials development from commercial model formulations.

36 MATERIALS SCIENCE↗