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At least 73 records · Page 4

Pressure-based process monitoring of direct-ink write material extrusion additive manufacturing

As additive manufacturing (AM) has become a reliable method for creating complex and unique hardware rapidly, the quality assurance of printed parts remains a priority. In situ process monitoring offers an approach for performing quality control while simultaneously minimizing post-production inspection. For extrusion printing processes, direct linkages between extrusion pressure fluctuations and print defects can be established by integrating pressure sensors onto the print head. In this work, the sensitivity of process monitoring is tested using engineered spherical defects. Pressure and force sensors located near an ink reservoir and just before the nozzle are shown to assist in identification of air bubbles, changes in height between the print head and build surface, clogs, and particle aggregates with a detection threshold of 60–70% of the nozzle diameter. Visual evidence of printed bead distortion is quantified using optical image analysis and correlated to pressure measurements. Importantly, this methodology provides an ability to monitor the quality of AM parts produced by extrusion printing methods and can be accomplished using commonly available pressure-sensing equipment.

36 MATERIALS SCIENCE↗

Development of Next Generation Hierarchical Hybrid Cu-Si anode Batteries via Direct-Ink Writing Application: End of (6th) Month Report - November 2025

Sustainable renewable energy continues to be in dire need to effectively combat global warming. Emerging technology for electric vehicles/ devices remains in high demand that is not only lower in cost, more efficient, but safer in comparison to commercial materials on the market. Although first-generation lithium-ion batteries have exhibited extensive commercial application, conventional graphite no longer meets this increasing demand as an efficient anode material. Due to the fact that graphite has a subpar theoretical specific capacity (372 mAh g -1 ), thus significant limitations in rate capability (for potential faster charging at higher C-rates currently commercially available.). Alternatively, silicon has gained significant attention as a superior candidate to potentially surpass graphite. Due to silicon’s exceedingly high theoretical capacity (4,200 mAh g -1 ) in comparison to standard graphite, its abundance thus in turn it’s low-cost, in addition to exhibiting a significantly low working potential (< 0.4 V vs Li/Li + ). However, one of the main (and most detrimental) challenges is silicon’s tendency to expand in volume (> 300%) upon discharge as it begins the lithiation process. As a direct result, it causes not only for the particles to both crack and pulverize under mechanical stress as the volume continues to expand and contract during cycling. Upon assembling the cell, it needs to undergo ‘charging’ for initially discharging/ ‘activating’ the cell, otherwise commonly known as the ‘formation’ step. As a result a solid electrolyte interface (SEI) layer begins to form at the anode surface because some of the electrolyte begins to react during the formation process. However, this (SEI) layer is deemed as a ‘protective’ interlayer because in theory it prevents further reaction as the cell continues to cycle. However, due to the volume change it causes significant degradation at the interface. As cracking starts to occur at the anode surface, it results in a ‘new’ altered surface with each cycle that causes further reaction with the electrolyte as a byproduct quickly consuming active Li/ and more electrolyte. Thus, fracturing this ‘protective layer,’ causing significantly higher impedance as a result, and in turn a decline in capacity due to active Li-loss. In addition to the active material exfoliating off from the current collector, further contributing to the steady decline in capacity and overall performance. Current state of the art Si-anode batteries on the market range between a maximum content of 5-10 Si wt%. It has been previously reported Tesla has utilized SiO x -C anodes containing 5 wt% Si within their ‘Model 3/ Model X’ electric vehicles. However, more recent ‘Model 3’ vehicles have started to incorporate 10 Si wt%, in which they were able to increase their energy density upwards by approximately 30%. Recent effort has been focused on continuing to increase the wt% of Si being utilized, eventually to 100 wt% of Si, to maximize the energy density even further.

36 MATERIALS SCIENCE↗

Nonlinear viscoelastic response of silicone additively manufactured direct ink write (DIW) foams under repetitive compression

To investigate dynamic fatigue behavior of foam in military protective applications, such as helmets, additively manufactured (AM) foams were compressively strained into the plateau region using a reduced design of experiments. A simple power law was found to govern the decline in dynamic stiffness (complex modulus) as the foams underwent the purchase order requirement of 10,000 cycles of small deformation in the plateau region. This rate of decline was newly found to correlate with the degree of nonlinearity in the material’s deformation, quantified using total harmonic distortion. Materials with low nonlinearity exhibited relatively stable stiffness across cycles, while those with high nonlinearity experienced greater losses. The observed nonlinearity depended on both applied stress and strain rate. A strong linear correlation (R 2 = 0.78) was identified between second-order nonlinearity and the time-dependent stiffness response. Two lattice structures were examined: face-centered tetragonal (FCT) and simple cubic (SC). The SC material exhibited higher total harmonic distortion (5%) and lower stiffness retention than the FCT (2%). In conclusion, these results suggest that for cyclic compression applications in a wide variety of industries such as packaging, personal protective equipment, or aerospace, selecting materials with lower stress and greater structural uniformity can enhance the stability of dynamic performance.

42 ENGINEERING↗

Combining direct ink writing with reactive melt infiltration to create architectured thermoelectric legs

Here, we present a new additive-reactive synthesis method where inks – cast into molds or 3D-additively extruded into architectured shapes – are reacted into intermetallic thermoelectric compounds. The new method, as demonstrated for equiatomic TiNiSn, combines: (i) extrusion printing (or casting) of inks containing Ni and Ti powders, (ii) debinding and reactive sintering to form a porous NiTi network, (iii) network infiltration with liquid Sn and subsequent reaction to synthesize the TiNiSn phase. Thin plates, created through this method, show high phase purity and low residual porosity. A thermoelectric figure of merit zT = 0.47 ± 0.05 is achieved at 800 K, within the broad range of values (zT= 0.3–1.0) reported for TiNiSn created via traditional powder hot-pressing methods. Layered TiNiSn microlattices – after 3D ink-extrusion printing and infiltration – exhibit high relative densities and minimal undesirable secondary phase content, with a Seebeck coefficient on par with the ink-cast TiNiSn plates, demonstrating that thermoelectric legs with far-ranging architectural freedom can be created additively with this novel reactive manufacturing method. Numerous other thermoelectric (and other) compounds, currently limited to basic geometries due to brittleness, are amenable to this new method based on a sequence of reactive sintering/infiltration of cast or ink-extruded precursors.

36 MATERIALS SCIENCE↗

Development of direct ink write radially graded alumina/zirconia

Functionally graded materials (FGMs) are of interest in multiple fields, yet many materials combinations are limited by coefficient of thermal expansion (CTE) mismatch. Here, a radially graded alumina/yttria-doped zirconia (Al 2 O 3 /8YZ) FGM is used to demonstrate processing strategies to mitigate CTE and sintering behavior differences between these oxides. FGM materials are especially sensitive to ink stability during printing, as all components (in this case, Al 2 O 3 and 8YZ) must be stabilized in the same dispersant or additive solution. Thus, this system is also ideal to demonstrate ink optimization best practices. Materials were characterized throughout processing to correlate the effects of common additives on both the ceramic particle suspensions and final sintered components. Aggregation observed in the initial additive-containing suspensions were present in the sintered component. The differences in sintering onset temperature and shrinkage rate resulted in internal stresses within the sintered component, which ultimately caused mechanical failure of the component under low stress. In conclusion, a processing strategy was recommended to mitigate the sintering behavior mismatch of alumina and 8 wt% yttria-stabilized zirconia.

Lamm, Benjamin W. [Oak Ridge National Laboratory (↗

A Dual Approach in Direct Ink Writing of Thermally Cured Shape Memory Rubber Toughened Epoxy

Bisphenol A-based epoxies are much used in a wide range of composite and coating applications due to their excellent thermomechanical properties. However, their 3D printability remains a challenge with most reported materials suffering from high brittleness and low toughness. In this work, we have described especially modified epoxy resins that enable 3D printing with both fast and slow curing rates. These materials exhibit greatly enhanced toughness, tunable thermomechanical properties, and excellent shape memory behavior. Two different printing systems, including a two-part static mixing printhead and a single extrusion printhead, were developed for fast- and slow-curing epoxies, respectively. The rheology of inks in both systems has been modified into printable thixotropic fluids with the aid of silica nanoparticles and other additives. Epoxide-functionalized telechelic polybutadiene was added into the resins, which are then introduced inside the epoxy network after cross-linking. The addition of polybutadiene rubber significantly improves the toughness (over 135%), fracture strain (over 200%), and shape memory behavior. By adding different amounts of the rubber telechelic, thermomechanical properties, including modulus, elongation, and Tg of epoxy, can be well controlled in a wide range to satisfy different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vapor-induced phase-separation-enabled versatile direct ink writing

Abstract Versatile printing of polymers, metals, and composites always calls for simple, economic approaches. Here we present an approach to three-dimensional (3D) printing of polymeric, metallic, and composite materials at room conditions, based on the polymeric vapor-induced phase separation (VIPS) process. During VIPS 3D printing (VIPS-3DP), a dissolved polymer-based ink is deposited in an environment where nebulized non-solvent is present, inducing the low-volatility solvent to be extracted from the filament in a controllable manner due to its higher chemical affinity with the non-solvent used. The polymeric phase is hardened in situ as a result of the induced phase separation process. The low volatility of the solvent enables its reclamation after the printing process, significantly reducing its environmental footprint. We first demonstrate the use of VIPS-3DP for polymer printing, showcasing its potential in printing intricate structures. We further extend VIPS-3DP to the deposition of polymer-based metallic inks or composite powder-laden polymeric inks, which become metallic parts or composites after a thermal cycle is applied. Furthermore, spatially tunable porous structures and functionally graded parts are printed by using the printing path to set the inter-filament porosity as well as an inorganic space-holder as an intra-filament porogen.

42 ENGINEERING↗

Direct ink writing of organic and carbon aerogels

Additive manufacturing is used to overcome inherent aerogel limitations. 3D printed aerogels simultaneously exhibit large capacitance and fast ion transport in millimeter-thick electrodes.

Chandrasekaran, Swetha↗

Curing inhibition and shelf stability in silicone formulations for direct ink writing

Various potential hydrosilylation inhibitors were incorporated into a silicone formulation for 3D printing. Different inhibitors resulted in peak cure temperatures from 42.8 to 180.3°C. The curing behavior of formulations with 1-ethynyl-1-cyclohexanol (ETCH), which exhibited a peak cure temperature of 98.4°C, was characterized for different ETCH concentrations and storage conditions. The curing was modeled using time temperature superposition, revealing an activation barrier of 89 kJ/mol. Overall, characterization resulted in a conservative recommended shelf life of 90 days. In conclusion, these studies offer insights into the stability of these formulations and the importance of inhibition for producing reliable, printable inks.

36 MATERIALS SCIENCE↗

Progress Summary: 12-Month Compression Set and Load Retention of Thermally Accelerated Aged Siloxane Specimens (Additively Manufactured by the Direct-Ink-Write (DIW) 3D Printing Technique) Was Measured

Motivation: Accelerated aging of polymeric materials is needed to predict their long-term mechanical functionality. Two key metrics used to evaluate their performance are compression set and load retention. A baseline(time=0)mechanical assessment was done prior to initiating the accelerated aging process to acquire initial thickness and load values for future calculation of compression set and load retention.Specimens are beingaged under compressive strain (13%for the current studies) at four different temperatures (25, 40, 55, and 70°C) for at least 1 year; compression set and load retention will be measured at various timepoints. Time-temperature superposition (TTS) will be applied to the isothermal data to obtain long-term predictions. Significance: Compression set is increasing with time and temperature, as expected. The increasing compression set is accompanied by decreasing load retention.The relativelylow compression set indicates the material is performing well.In a previous aging study, the legacy S5370 RTV foam exhibited 40% relative compression set after 12 months at 70°C, which is more than twice that of the DIW material. Progress:Data has been acquired out to the 12-month timepoint. Relative compression set and load retention versus time are shown in Fig. 1.A technical issue with the method of measuring load retention was discovered and previously reported load retention values have been adjusted; the current load retention values are estimates. TTS predictions are shown in Fig. 2.

36 MATERIALS SCIENCE↗

Progress Summary: 17-Month Compression Set and Load Retention of Thermally Accelerated Aged Siloxane Specimens (Additively Manufactured by the Direct-Ink-Write (DIW) 3D Printing Technique) was Measured

Accelerated aging of polymeric materials is needed to predict their long-term mechanical functionality. Two key metrics used to evaluate their performance are compression set and load retention. A baseline (time = 0) mechanical assessment was done prior to initiating the accelerated aging process to acquire initial thickness and load values for future calculation of compression set and load retention.

36 MATERIALS SCIENCE↗

Radiation Aging of Siloxane Specimens Additively Manufactured by the Direct-Ink-Write (DIW) 3D Printing Technique

Accelerated aging of polymeric materials is needed to predict their long-term mechanical functionality. Two key metrics used to evaluate their performance are compression set and load retention. Previously, DIW siloxane specimens were subjected to radiation doses between 1 and 10 Mrad while under compression, followed by measurement of thickness (to calculate compression set) and load deflection (to calculate load retention). To support a modeling effort, a range of lower doses is needed.

36 MATERIALS SCIENCE↗

In Situ Monitoring of Direct Ink Write Process Using Electromagnetic Resonant Coupling

Additive manufacturing (AM) of multi-material objects enables the design of complex 3D architectures such as printed electronics and devices. The ability to detect the composition of multi-material printed inks in real time is an emerging need for a wide range of manufacturing applications. This study demonstrates the feasibility of using an in situ sensor to locally measure the composition of inks as they are being printed to facilitate greater control over the resulting properties and functionality of printed materials. Dielectric properties of microscale embedded metal particles in a dielectric matrix are measured and characterized as a function of particle size, shape, volume percentage and frequency. Results show that particle shape has a much greater influence on impedance measurements than the particle size. Measurements are found to agree with calculations based on an anisotropic Maxwell-Garnett dielectric function model. The resulting data can be used to generate a calibration curve correlating metal loading with impedance or capacitance and thus applied as an in situ sensor for compositional measurements during extrusion-based AM.

36 MATERIALS SCIENCE↗