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At least 271 records · Page 15

3D printing of void-free glass monoliths: rheological and geometric considerations

Direct ink writing (DIW) is a versatile additive manufacturing technique capable of printing 3D architectures from a broad range of materials. The key advantage of DIW is the ability to spatially control both the architecture and the composition of the printed part, which enables the production of components with previously unachievable combinations of functionalities. One emergent application space for DIW has been in additively manufactured glass optics, where a “green body” is patterned layer-by-layer by extruding a silica-based slurry through a microfluidic nozzle and then thermally consolidated to transparent glass. A critical aspect of the process is ensuring that the printed part is completely free of voids that can occur in the interstitial spaces between the extruded filaments. This outcome is governed by the interplay between ink rheology and strains imposed by the printing process and geometric packing of the filaments. Here, we explore the strain- and rate-dependent deformation events in the DIW process to determine conditions that enable the printing of void-free monoliths without sacrificing shape fidelity. We focus on yield stress fluids consisting of fumed silica nanoparticles dispersed in organic solvents at varied volume fractions to control the rheological properties. We investigate the printability of these ink materials as a function of print process variables and devise the appropriate dimensionless parameters that capture the geometry-dependent and rate-dependent effects on the deformation of the extruded ink. Lastly, we use these scaling arguments to construct a phase diagram for void-free monolith printability.

36 MATERIALS SCIENCE↗

La–Sr–Co oxide catalysts for oxygen evolution reaction in anion exchange membrane water electrolyzer: The role of electrode fabrication on performance and durability

Anion exchange membrane water electrolysis is an attractive technology for low-cost generation of “green” hydrogen by combining the use of noble metal-free catalysts with pure water feed. By thus addressing main drawbacks of the liquid alkaline electrolysis and proton exchange membrane water electrolysis, anion exchange membrane water electrolysis stands an excellent chance of replacing the two technologies. The development of active and stable platinum group metal (PGM)-free catalysts for oxygen evolution reaction (OER) is crucial for making anion exchange membrane water electrolyzers (AEMWEs) practical. For this work, we synthesized, characterized and tested two La–Sr–Co oxide-based OER catalysts. First, we characterized the catalysts by XRD, SEM, and N 2 physisorption and assessed their OER activity in a three-electrode cell. Next, we focused on electrode fabrication, demonstrating the importance of catalyst-ink application to the porous transport layers (PTLs) and a key role of adding a binder to the catalyst ink to prevent the catalyst detachment from the PTL in pure water. We tested three membrane electrode assemblies prepared using different formulations of the anode catalyst ink. The results show that the optimum ink formulation is essential for the performance on pure-water feed by maximizing OH - conductivity of the catalyst layer and catalyst-membrane interface.

47 OTHER INSTRUMENTATION↗

Simulation of two nanoparticle melting to understand the conductivity drop of 3D-printed silver nanowires

The future flexible sensor technology will require low-temperature, fast processing 3D printing techniques that will rely heavily on the quality of nanoparticle (NP) Ink. Electrical conductivity has been found to decrease in majority of the 3D printed electronic wires. Herein we report a fundamental understanding in drop of electrical conductivity in processed silver (Ag) line wire, generally found in Ag-nanoparticle Ink, using large-scale atomistic molecular dynamics (MD) simulations of sintering of five different sizes of Ag NPs. To preserve the high conductivity of pure silver wires, the integrity of the pristine face-centered cubic (FCC) crystalline structure must be retained in the processed line wires. Simulations show that the pristine Ag FCC structures of the nanoparticles are not recovered after melting and resolidification, instead, the resolidified material is paracrystaline. The breakdown of pristine FCC structures might be the cause of the drop in conductivity of processed Ag wires. Simulation results suggest that the intermediate size nanoparticles retain highest percentage of the pristine silver face-centered cubic (FCC) structure after pulse treatments. Our results show that the most promising Ag-Ink should contain smaller to medium size silver NPs that can retain FCC structure after 3D printing of the Ag-Ink.

42 ENGINEERING↗

All 2D Material Printed Diodes and Circuits on Paper for Sustainable Electronics

Sustainable electronics aim to reduce environmental impact by using ecofriendly materials, energy-efficient manufacturing, and recyclable components. However, existing approaches rely on complex, resource-intensive methods, rare metals, or nanomaterials with limited stability as well as plastic substrates, raising sustainability issues. Solution-processed two-dimensional (2D) materials offer a promising alternative: water-based and biocompatible conductive, semiconductive, and insulating 2D material inks can be produced with scalable techniques and are suitable for the fabrication of fully printed devices on low-cost and biodegradable paper substrates. However, 2D material only and fully printed diodes on paper have not yet been reported. Here, we demonstrate fully inkjet-printed 2D material-based diodes on paper using metal-insulator-semiconductor and metal-insulator-metal-semiconductor architectures. Water-based graphene and MoS2 inks, prepared by liquid-phase exfoliation, are used for the metallic and insulating films, while electrochemical exfoliation is used to produce the semiconducting MoS2 ink. The highest forward-to-reverse current ratio obtained is 330 (at ±2 V), while the forward current density is 1 mA/cm2 (at 1 V), making the diode performance comparable to the best solution-processed diodes reported so far. However, in contrast to previous works, fabrication occurs entirely at room temperature and ambient pressure, without using high-pressure sputtering, thermal evaporation, and any precious metal ink. The devices maintain stable performance under bending up to strain of 4% over 10,000 cycles. Finally, the diodes are successfully integrated with other 2D-material based electrical components to realize fully printed RC circuits, differentiators, integrators, and AC-to-DC converters onto paper, hence demonstrating the suitability of our approach for sustainable and disposable integrated circuits.

2D materials↗

Spatially programmed alignment and actuation in printed liquid crystal elastomers

Liquid crystal elastomers (LCEs) exhibit reversible shape morphing behavior when cycled above their nematic-to-isotropic transition temperature. During extrusion-based 3D printing, LCE inks are subjected to coupled shear and extensional flows that can be harnessed to spatially control the alignment of their nematic director along prescribed print paths. Here, we combine experiment and modeling to elucidate the effects of ink composition, nozzle geometry, and printing parameters on director alignment. From rheological measurements, we quantify the dimensionless Weissenberg number ( Wi ) for the flow field each ink experiences as a function of printing conditions and demonstrate that Wi is a strong predictor of LCE alignment. We find that director alignment in LCE filaments printed through a tapered nozzle varies radially when Wi < 1, while it is uniform when Wi ≫ 1. Based on COMSOL simulations and in operando X-ray measurements, we show that LCE inks printed through nozzles with an internal hyperbolic geometry exhibit a more uniform director alignment for a given Wi compared to those through tapered nozzles. Concomitantly, the stiffness along the print direction and actuation strain of printed LCEs increases substantially under such conditions. By varying Wi during printing through adjusting the flow rate “on the fly”, LCE architectures with uniform composition, yet locally encoded shape morphing transitions can be realized.

36 MATERIALS SCIENCE↗

Understanding and mitigating process drift in aerosol jet printing

Aerosol jet printing offers a versatile, high-resolution prototyping capability for flexible and hybrid electronics. Despite its rapid growth in recent years, persistent problems such as process drift hinder the adoption of this technology in production environments. Here we explore underlying causes of process drift during aerosol jet printing and introduce an engineered solution to improve deposition stability. In this work it is shown that the ink level within the cartridge is a critical factor in determining atomization efficiency, such that the reduction in ink volume resulting from printing itself can induce significant and systematic process drift. By integrating a custom 3D-printed cartridge with an ink recirculation system, ink composition and level within the cartridge are better maintained. This strategy allows extended duration printing with improved stability, as evidenced by 30 h of printing over 5 production runs. This provides an important tool for extending the duration and improving reliability for aerosol jet printing, a key factor for integration in practical manufacturing operations.

36 MATERIALS SCIENCE↗

FY2020 Annual Report on Subcontract B631779 with UC Berkeley: Reactive Precursors Additive Manufacturing Report

This work succeeded in reaching each of the stated milestones for developing, printing, reacting, and characterizing the uranium carbide final products. Leveraging experience gained from creating magnesium oxide inks (milestone #1) and prior reactive precursor work with boron carbide (milestone #2) a uranium carbide reactive precursor ink was developed. The chosen composition of ink utilized a mixture of wax, petrolatum, and stearic acid as the binder. The reactive precursor portion of the ink was comprised of uranium oxide and nano particle activated carbon for production of uranium carbide via carbothermal reduction. Following an in-air burnout of the binder at 160C the printed samples were reacted and sintered at 1750C in an argon environment induction furnace. The resulting product has an open porosity dense, foam-like internal structure with a calculated density of 89% in the solid fraction.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Scalable Approaches to Address Thermomechanical and Chemical Instabilities in Metal Halide Perovskites

We will discuss our group’s recent efforts to address the thermomechanical and chemical instabilities of metal halide perovskites through multiple approaches. These approaches cover several length scales and aim to provide better understanding of behavior in all stages of processing—i.e., precursor behavior in inks, growth behavior of films during printing, and resulting optoelectronic properties and robustness of perovskite films and devices. We will highlight our efforts toward scalable printing of high-quality perovskite using the method recently invented by our group restricted area printing by ink drawing (RAPID). Additionally, we will discuss how molecular additives in precursor inks can influence the stability of the inks and resultant films. Finally, we will also describe our recent progress in addressing the poor mechanical toughness of perovskite using multifunctional nanofiber reinforcements. Together, all of these concepts are complimentary and compatible with scalable printing of perovskites and a necessary step towards developing a viable technology with long operational lifetimes.

Printz, Adam↗

Impact of Synthesis and Aging on Titanium Carbide MXenes for Printed Microsystems

This work investigates the long-term electrical stability of Ti3C2Tx MXene Inks under accelerated aging conditions. Inks were synthesized from commercial MAX-Phase precursors, drop-cast onto custom PCB’s and monitored automated in-situ measurements. Samples aged at 85°C/85% RH, 85°C/0% RH and ambient conditions revealed distinct degradation trends. Wet aged inks showed rapid resistance increased while etched formulations exhibited long term stability. These findings highlight the influence of synthesis stage and environmental exposure on MXene Inks reliability, offering critical insights for printed MEMS and sensor applications. Ongoing measurements extend the aging timeline beyond prior studies, marking the longest evaluation under accelerated aging conditions to date.

Aging↗

Approaching the Practical Conductivity Limits of Aerosol Jet Printed Silver

Previous efforts to directly write conductive metals have been narrowly focused on nanoparticle ink suspensions that require aggressive sintering (>200°C) and result in low-density, small-grained agglomerates with electrical conductivities <25% of bulk metal. Here, we demonstrate aerosol jet printing of a reactive ink solution and characterize high-density (93%) printed silver traces having near-bulk conductivity and grain sizes greater than the electron mean free path, while only requiring low temperature (80°C) treatment. We have developed a predictive electronic transport model which correlates the microstructure to the measured conductivity and identifies a strategy to approach the practical conductivity limit for printed metals. Our analysis of how grain boundaries and tortuosity contribute to electrical resistivity provides insight into the basic materials science that governs how an ink formulator or process developer might approach improving the conductivity. Transmission line measurements validate that electrical properties are preserved up to 20GHz, which demonstrates the utility of this technique for printed RF components. Finally, this work reveals a new method of producing robust printed electronics that retain the advantages of rapid prototyping and three-dimensional fabrication while achieving the performance necessary for success within the aerospace and communications industries.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Refractive Index and Abbe Number Tuning via 3D Printable Optical Quality Silica–Titania–Germania Glasses

The development of optical quality GeO 2 –TiO 2 –SiO 2 glasses compatible with direct ink writing (DIW) 3D printing is reported in this study. Colloidal GeO 2 and TiO 2 –SiO 2 core–shell feedstocks are prepared by a sol–gel method and converted to printable inks for DIW. Printed inks are subsequently densified to glass using heat treatment at temperatures up to 1100 °C in air. A series of print‐compatible glass compositions are prepared, yielding transparent glass with the highest refractive index n = 1.576. Herein, it is shown that more TiO 2 can be incorporated into the glass without haziness or scattering through the addition of GeO 2 . The mechanisms for this are discussed, and it is shown that crystallization persists in these glasses despite the lack of visible light scattering. Finally, the combination of both TiO 2 and GeO 2 into a ternary glass also is used to independently tune the dispersion properties of the glass, as demonstrated by measured refractive indices and Abbe numbers, which has potential implications for 3D‐printed optics.

36 MATERIALS SCIENCE↗

Processing and mechanical characterization of short carbon fiber-reinforced epoxy composites for material extrusion additive manufacturing

Fiber-reinforced polymer composites have been extensively utilized in recent years as feedstock materials for material extrusion additive manufacturing (AM) processes to improve strength, stiffness, and functionality of printed parts over unfilled printed polymers. However, the widespread adoption of AM of fiber-reinforced polymer composites requires a deeper understanding of the process-structure-property relationships in printed components, and such relationships are not well understood yet. Fiber length is critically important to the mechanical performance of short fiber composites, but very few studies to-date have focused on how the fiber length distribution (FLD) evolves during processing of composite feedstocks and how this evolution affects printing behavior and mechanical properties in 3D-printed composites. Here, FLD is measured for carbon fiber reinforced epoxy composites over a wide range of ink compositions and shear mixing times, and the distributions are fit with a Weibull-type distribution function. The effects of FLD on the tradeoff between ink processability, ink rheology, printing behavior and mechanical properties are investigated. Furthermore, the effects of printing parameters (nozzle size and print speed) on mechanical anisotropy and fiber orientation distribution (FOD) in printed composites are explored. Mechanical properties of printed composites are characterized via 3 pt-flexural testing, and microstructure is investigated using optical and scanning electron microscopy (SEM), and x-ray computed tomography. Finally, the fitted Weibull parameters are fed into a composite model that incorporates FLD and FOD, and model predictions are found to be in excellent agreement with experimental observations.

3D printing↗

EXPERIMENTAL STUDY ON COST-EFFECTIVE ADDITIVE MANUFACTURING OF SILICA AEROGEL

The conventional aerogel insulation material manufacturing from supercritical drying suffers from issues of massive energy consumption and prolonged processing time. With the consideration of large market demand of the aerogel insulation material in the next decade, a low-cost and scalable fabrication technique is highly desired. In this paper, a direct ink writing (DIW) method is used to three-dimensionally fabricate the silica aerogel insulation material, followed by ambient pressure drying. Compared to the supercritical drying and freeze drying, the reported method significantly reduces the fabrication time and costs. The cost-effective DIW technique offers the capability to print complex hollow internal structure, coupled with the porous structure, is found to be beneficial to the thermal insulation property. The addition of fiber to the ink assures the durability of the fabricated product. The foam ink preparation methods and the printability are demonstrated in this paper, along with the printed samples for characterizing thermal insulation properties and mechanical properties.

42 ENGINEERING↗

Innovative Design and Manufacturing of 2.5D Battery with High Energy and Power Density (Final Report)

The goal of this project is to develop cathode inks, to be used in additive manufacturing (AM), that lead to a low-cost, fast manufacturing processes for a new type of non-planar, 2.5D lithium-ion battery (LIB). 2.5D batteries, comprised of a high-aspect-ratio 3D electrode combined with a 2D planar electrode, can simplify the fabrication process because there is no need for the alignment steps seen in traditional 3D batteries. For the success of the two AM processes identified in this project, development of cathode inks is key component because it allows for both platforms to be evaluated in achieving high performance batteries and ease of manufacturing. The two AM processes explored in this project are direct ink writing (DIW) and templating. Both of these processes have been shown to be successful in depositing materials for traditional LIBs and will be used now for the 3D array electrode configuration as part of the 2.5D battery.

25 ENERGY STORAGE↗

Carbon Fiber and Syntactic Foam Hybrid Materials via Core–Shell Material Extrusion Additive Manufacturing

Abstract Biological materials often employ hybrid architectures, such as the core–shell (C–S) motif present in porcupine quills and plant stems, to achieve unique specific properties and performance. Drawing inspiration from these natural materials, a new method to fabricate lightweight and stiff C–S architected filaments is reported. Specifically, a C–S printhead conducive to printing highly loaded fiber‐filled inks, as well as a new low‐density syntactic foam ink, are utilized to 3D‐print C–S architectures consisting of a syntactic epoxy foam core surrounded by a stiff carbon fiber‐reinforced epoxy composite shell. Effective printing of test specimens and structures with controlled geometry, composition, and architecture is demonstrated. The new foam ink exhibits density as low as 0.68 g cm −3 and C–S structures exhibit up to 25% higher specific flexural stiffness ( E 1/3 /ρ) than either constituent alone. Finally, a new mechanical model is presented to predict this performance improvement while accounting for potential eccentricity of the core.

Pack, Robert C.↗

Fully R2R-Printed Carbon-Nanotube-Based Limitless Length of Flexible Active-Matrix for Electrophoretic Display Application

A limitless-length flexible active-matrix implies that virtually any surface can be rendered into an interactive medium when laminated with electrophoretic or organic light-emitting diode sheets. However, performance, cost, and size limitations of current fabrication technologies and semiconducting materials, typically utilized in thin film transistor (TFT) active matrices (TFT-AMs), have hindered progress, thus preventing the realization of fully printed TFT-AMs on a plastic roll. Here, a new high-purity semiconducting single-walled carbon nanotube (s-SWCNT) ink is prepared by first isolating 99.9% pure s-SWCNTs via conjugated polymer extraction, and then utilizing a ligand-exchange method to formulate a novel hydrophilic gravure-compatible semiconducting ink. Based on the s-SWCNT ink, a fully additive manufacturing process using roll-to-roll (R2R) gravure printing enables the fabrication of a flexible TFT-AM, overcoming performance, cost, and size limitations. TFT-AMs with 10 to 40 PPI resolution where average mobility of 0.23 ± 0.12 cm 2 V –1 s –1 , average on–off ratio of 10 4.1 , and threshold voltage variation of ±13% are attained. As a proof of concept, an inexpensive and flexible electrophoretic display is demonstrated by simply laminating an electrophoretic sheet onto the R2R gravure-printed s-SWCNT-based TFT-AM.

36 MATERIALS SCIENCE↗

Revealing meso-structure dynamics in additive manufacturing of energy storage via operando coherent X-ray scattering

3D printing is an emerging technology for the fabrication of energy storage devices, offering advantages over traditional manufacturing methods. However, optimization and design of such devices requires an understanding of the meso-structure formation during the 3D printing process. This study utilizes operando coherent X-ray scattering, X-ray Photon Correlation Spectroscopy (XPCS), to study the spatiotemporally-resolved far-from-equilibrium dynamics during direct ink writing 3D printing. Here, Lithium Titanate (LTO) based ink is prepared and rheologically tested for its shear-thinning properties. Two-time intensity-intensity functions are calculated to be used in subsequent quantitative analysis, which allows for an overall characterization of the dynamics, description of an initial fast decorrelation and identification of sudden rearrangements of subdomains of the sample. The results show the dynamics to be anisotropic, spatiotemporally heterogenous and marked by distinct rearrangement events, all of which impact the electrochemical performance of energy storage devices. The studied 3D printing ink is used to fabricate electrodes which are then electrochemically tested, showing good performance in cycling and retaining structural integrity. This work furthers the understanding of the far-from-equilibrium material dynamics during 3D printing, giving quantitative characterization of this process, and highlights aspects of structure formation relevant to the electrochemical performance of the resultant energy storage device.

36 MATERIALS SCIENCE↗