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At least 73 records · Page 4

3D-Printable Inks for Energy and Environmental Applications

Partnering additive manufacturing (3D printing) with functional nanomaterial-based inks has the potential to push the properties and performance of advanced materials beyond previous capabilities. This is particularly true in energy and environmental applications. Graphene, 2D materials, and ceramic-based inks, when coupled with 3D printing technologies like Direct Ink Writing (DIW), also called “robocasting,” have shown promise to greatly enhance the performance of batteries, supercapacitors, reactors, and separator devices. Robocasting enables the printing of large-scale electrodes for energy applications with micron resolution by using high concentration viscous inks.

36 MATERIALS SCIENCE↗

Fire-retardant decorative inks for aircraft interiors

Commercial and experimental fire retardants were screened as potential fire retardants for acrylic printing inks used on aircraft interior sandwich panels. The fire retardants are selected according to their physical properties and their thermostabilities. A criterion for selecting a more stable fire retardant is established. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) are used to determine thermostabilities. Results show that the fire retardant formulations are more thermally stable than the acrylic ink control. It is determined that an ink formulation containing a brominated phenol and carboxy-terminated butadiene acrylonitrile which has been modified with a brominated polymeric additive (BPA), yields the highest limiting oxygen index (LOI) of all the compounds tested. All of the fire-retardant formulations have a higher oxygen index than the baseline acrylic ink.

Kourtides, D. A.↗

Ink jet assisted metallization for low cost flat plate solar cells

Computer-controlled ink-jet-assisted metallization of the front surface of solar cells with metalorganic silver inks offers a maskless alternative method to conventional photolithography and screen printing. This method can provide low cost, fine resolution, reduced process complexity, avoidance of degradation of the p-n junction by firing at lower temperature, and uniform line film on rough surface of solar cells. The metallization process involves belt furnace firing and thermal spiking. With multilayer ink jet printing and firing, solar cells of about 5-6 percent efficiency without antireflection (AR) coating can be produced. With a titanium thin-film underlayer as an adhesion promoter, solar cells of average efficiency 8.08 percent without AR coating can be obtained. This efficiency value is approximately equal to that of thin-film solar cells of the same lot. Problems with regard to lower inorganic content of the inks and contact resistance are noted.

Teng, K. F.↗

The Effect of Jetting Parameters on the Performance of Droplet Formation for Ink-Jet Rapid Prototyping

Heinzl et al. (1985) reports that experiments in ink-jets to produce drawings or signals occurred as early as 1930. Various companies such as IBM and Pitney-Bowes have conducted extensive studies on these devices for many years. Many such reports are available in such journals as the IBM Journal of Research and Development. While numerous articles have been published on the jetting characteristics of ink and water, the literature is rather limited on fluids such as waxes (Gao & Sonin 1994) or non-water based fluids (Passow, et al. 1993). This present study extends the knowledge base to determine the performance of molten waxes in "ink-jet" type printers for rapid prototyping. The purpose of this research was to qualitatively and quantitatively study the droplet formation of a drop-on-demand ink-jet type nozzle system for rapid prototyping.

Helmer, Wayne↗

Real-time process monitoring for direct ink write additive manufacturing

Direct ink write (DIW) printing of reactive resins presents a unique challenge due to the time-dependent nature of the rheological and chemical properties of the ink. As a result, careful print optimization or process control is important to obtain consistent, high quality prints. The present invention uses a flow-through characterization cell for in situ chemical monitoring of a resin ink during DIW printing. Additionally, in-line extrusion force monitoring can be combined with off-line post inspection using machine vision. By combining in-line spectroscopy and force monitoring, it is possible to follow reaction kinetics (for example, curing of a reactive resin) and viscosity changes during printing, which can be used for a closed-loop process control. Additionally, the capability of machine vision to automatically identify and quantify print artifacts can be incorporated on the printing line to enable real-time, AI-assisted quality control of the printed products. Together, these techniques can form the building blocks of an optimized process control strategy when complex reactive ink must be used to produce printed hardware.

Cook, Adam W.↗

Direct Metallization with Reactive Inks – Assessment of Reliability and Process Sensitivities

This project will reduce silver consumption in photovoltaic cells by a factor of almost ten – from 95 mg/cell (the median across technologies) to 10 mg/cell. To achieve this goal, we will replace screen-printed silver pastes with contact dispensed reactive inks that produce lower resistivity metallizations at lower temperatures and with thinner films. This project will generate the understanding necessary to scale this reactive ink technology from the bench-scale to commercial throughputs. Specifically, it will combine fundamental understanding on physics and chemistries involved in contact printing of reactive inks with detailed performance and reliability studies to quantify how tightly processing parameters need to be controlled in order to reliably metallize high efficiency solar cells at commercial throughputs of 36,000 cells/hour.

14 SOLAR ENERGY↗

Recent advances in ink-based additive manufacturing for porous structures

The use of porous structures is an ancient wisdom, people found its importance ever since we began to understand nature. The evolution of porous structure gives rise to multi-scale (combined nano-, micro-, and macro-) porous networks. Traditional manufacturing technologies have challenges in creating shape-complex and conformable porous structures for real-world applications. Additive manufacturing (AM) with the capability of assembling various materials with complex and customized architectures is rapidly developing. With the advancement of material development, the integration of AM and porous structure offers unparalleled and emerging opportunities for concept-to-design-to-fabrication of multi-scale porous networks, enabling the multi-functionalities of the 3D printed specimen and broadening its applications. In this work, we provide a comprehensive review of the state-of-the-art ink-based AM techniques for 3D printing porous structures. The ink design principle, ink composition, and printability are thoroughly discussed. The methodologies of various AM technologies for porous structures are analyzed. Readers can find a clear experimental guidance toward 3D printing multi-scale porous structures. The synergistic and collective merits of additive manufacturing and porous structure are highlighted and systematically discussed in this review. The challenges and promises of this field for future research are also outlined.

36 MATERIALS SCIENCE↗

Direct ink writing of aqueous-based Gadolinium (III) oxide slurries

Gadolinium (III) oxide (gadolinia, Gd 2 O 3 ) has recently been identified as an intriguing material for applications in the medical, solid oxide fuel cell, and nuclear industries. This interest drives the need for developing and understanding manufacturing techniques that can produce dense Gd 2 O 3 structures. Direct ink writing (DIW), an extrusion-based additive manufacturing method, has also garnered interest because of its capability to produce dense ceramic parts with increased complexity in an economical manner. In this study, DIW was explored as a manufacturing technique for Gd 2 O 3 . Experiments were performed to develop Gd 2 O 3 bearing inks capable of being processed via DIW. Ink solids loading and sintering temperatures were varied to assess their impact on the final density and microstructure. Optimum sintering conditions are proposed and were experimentally verified at a dwell temperature of 1500°C. Gd 2 O 3 samples were successfully manufactured using DIW, achieving densities greater than 96 % of the theoretical density.

36 MATERIALS SCIENCE↗

On the melt pool dynamic of voxel-controlled metal matrix composites via hybrid additive manufacturing: Laser powder bed fusion and ink-jetting

In this study, the effect of the addition of reinforcement nanoparticles to the 316L matrix by adopting ex-situ and in-situ method (drop on demand jetting) to produce 316L/Al 2 O 3 nanocomposite was investigated. In the ex-situ method, the Al 2 O 3 nanoparticles (NPs) were lightly mixed with 316L powder and processed by laser powder bed fusion. In the in-situ method, an ethanol-based ink containing Al 13 nanoclusters (NCs) was added to 316L powder and then processed by laser. Both ex-situ and in-situ method produced nanocomposites with Al-Si-Mn-O-enriched precipitations within the 316L matrix. The addition of NPs/NCs to the 316L matrix, altered the geometrical characteristic of the single-track melt pools. At the same laser power, with increasing the amount of Al 2 O 3 NPs and Al 13 NCs the melt pool deepened due to reduced thermal conductivity and prolonged liquid presence. Further, as a result, 316L/1 wt% Al 13 NCs deposited single track showed larger grains in comparison to 316L single track. At a high laser power of 150W, the Marangoni flow and the buoyancy force caused the nanoparticles to agglomerate and float to the top surface of tracks; therefore, the wt% fraction of precipitation was drastically reduced due to the loss of Al. The 316L/Al 2 O 3 NPs and 316L/Al 13 NCs exhibited the microhardness of 285 ± 13 HV and 293 ± 7 HV, respectively, higher than the deposited 316L single track, 265 ± 15 HV. Lastly, a hybrid LPBF+ink-jet printer was adopted to selectively change the composition of different zones by adding Al 13 NCs ink to 316L and producing a voxel-controlled metal matrix composite.

316L↗

Effects of Ink Formulation on Construction of Catalyst Layers for High-Performance Polymer Electrolyte Membrane Fuel Cells

Rational design of catalyst layers in a membrane electrode assembly (MEA) is crucial for achieving high-performance polymer electrolyte membrane fuel cells. Establishing a clear understanding of the property (catalyst ink)–structure (catalyst layer)–performance (MEA) relationship lays the foundation for this rational design. Here, a synergistic approach was taken to correlate the ink formulation, the microstructure of catalyst layers, and the resulting MEA performance to establish such a property–structure–performance relationship. The solvent composition (n-PA/H 2 O mixtures) demonstrated a strong influence on the performance of the MEA fabricated with an 830-EW (Aquivion) ionomer, especially polarization losses of cell activation and mass transport. The performance differences were studied in terms of how the solvent composition affects the catalyst/ionomer interface, ionomer network, and pore structure of the resulting catalyst layers. The ionomer aggregates mainly covered the surface of catalyst aggregates acting as oxygen reduction reaction active sites, and the aggregate sizes of the ionomer and catalyst (revealed by ultrasmall angle X-ray scattering and cryo-transmission electron microscopy) were dictated by tuning the solvent composition, which in turn determined the catalyst/ionomer interface (available active sites). In n-PA/H 2 O mixtures with 50~90 wt % H 2 O, the catalyst agglomerates could be effectively broken up into small aggregates, leading to enhanced kinetic activities. The boiling point of the mixed solvents determined the pore structure of ultimate catalyst layers, as evidenced by mercury porosimetry and scanning electron microscopy. For mixed solvents with a higher boiling point, the catalyst–ionomer aggregates in the ink tend to agglomerate during the solvent evaporation process and finally form larger catalyst–ionomer aggregates in the ultimate catalyst layer, resulting in more secondary pores and thus lower mass transport resistance. Both the enlarged catalyst/ionomer interface and appropriate pore structure were achieved with the catalyst layer fabricated from an n-PA/H 2 O mixture with 90 wt % H 2 O, leading to the best MEA performance.

25 ENERGY STORAGE↗

Overcoming efficiency and cost barriers for large-area quantum dot photovoltaics through stable ink engineering

The bottom-up construction of electronics from colloidal quantum dots (CQDs) could innovate nanotechnology manufacturing through printing. However, the unstable and expensive semiconductive CQD inks make the scaling up of CQD electronics challenging. Here, in this study, we develop a strategy for engineering the solution chemistry of lead sulfide (PbS) CQD inks prepared from a low-cost direct synthesis method. By creating an iodine-rich environment in weakly coordinating solvents, we convert the iodoplumbates into functional anions, which condense into a robust surface shell. The fully charged electrostatic surface layer prevents aggregation and epitaxial fusion of CQDs, yielding stable inks. By eliminating the fusion-induced inter-band states, we print a compact CQD film with uniformity in three dimensions, flattened energy landscape and improved carrier transport. We achieved a certified efficiency of 13.40% on 0.04 cm 2 cells, with a 300-fold increase in active area, scaling up to a 12.60 cm 2 module with a certified efficiency of 10%.

14 SOLAR ENERGY↗

Dry electrodes with a printed cellulose–graphene ink for low-profile strain sensors in electromyography

Dihydrolevoglucosenone, commonly known as Cyrene, is a renewable and fully biodegradable cellulose-waste derived, environmentally friendly solvent, presenting a non-toxic alternative to N-methyl-2-pyrrolidone (NMP). Currently, solution-based processing of graphene and other similar van der Waals solids favor toxic solvents such as NMP, limiting their use for biosensing. However, with the use of Cyrene, bio-compatible printable devices are possible, and studies have already demonstrated its use in temperature and other biosensing methods through screen-printing. Screen-printing unfortunately often requires masks that constrain the minimum acquirable feature size to be above hundreds of centimeters and wastes material, adding to process complexity and cost. Conversely, inkjet-printing is an attractive alternative for the maskless patterning of hierarchically assembled structures, with micron length scales attainable. Graphene's high conductivity positions it ideally for long-wear sensors such as dry electrodes or respiration monitors. Here, we demonstrate the potential of Cyrene-based graphene inks through few-layer inkjet printing on flexible substrates for the first time, to produce non-toxic conductors toward a strain-mediated mechanism for biosensing, used to detect bodily motion for wearable electronics. The challenges overcome in this study include engineering ink chemistry and printing parameters such that Cyrene's relatively high viscosity compared to typical inkjet solvents, still allows for droplet ejection in a conventional material printer, yielding well-resolved clean line-edges in contrast to other solvents that exhibit diffuse line-edges possibly from stray droplets and ink-splashing. Temperature-dependent transport measurements on the inkjet-printed Cyrene-based graphene films showed the conductivity to be largely temperature-invariant but at lower temperatures below 100 K, conductivity decreased, likely as a result of increased inter-membrane separation arising from thermal contraction. Additionally, temperature-dependent Raman spectroscopy showed the red-shift in the G-band, 2D-band and D-band peaks, as temperature increased. As a result, by validating flexion motion detection of the proximal interphalangeal joint demonstrated in this study, our work is the first of its kind to successfully additively manufacture inkjet-printed Cyrene-based graphene strain sensors on flexible substrates for bio-sensing and wearables.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ink Casting and 3D‐Extrusion Printing of Yb 14 MnSb 11 for High‐Temperature Thermoelectric Material

Abstract Complex shapes are created from Yb 14 MnSb 11 , a high‐temperature thermoelectric Zintl phase, via a two‐step process: i) layer‐by‐layer 3D‐extrusion of ink containing partially‐reacted powders which are ball‐milled from a blend of Yb, MnSb, and Sb powders; ii) heat treatment to synthesize the ternary compound Yb 14 MnSb 11 and densify the extruded powders. A high phase purity for Yb 14 MnSb 11 (83–94%) is achieved in both cast and 3D‐extruded ink specimens via a solid‐state reaction between Yb, MnSb, and Yb 4 Sb 3 during reactive sintering. Pressure‐free sintering at temperatures of 1200–1400 °C densifies the powders to 82% relative density but can also induce the decomposition of the Yb 14 MnSb 11 phase due to Yb sublimation. A process window with optimized sintering temperature and time is identified, achieving both low porosity and high phase purity and reaching a maximum zT = 0.61 at 1000 °C, about half of the maximum zT value for bulk Yb 14 MnSb 11 made via conventional processes (pressure sintering of precursor powders). The present approach – direct ink writing of ball‐milled powders, combined with reactive sintering – is a scalable and affordable method to fabricate thermoelectric legs with intricate 3D shapes, for enhanced performances in high‐temperature thermoelectric applications.

Chen, Ming [Department of Materials Science &amp, ↗

Aerosol‐Jet‐Printable Covalent Organic Framework Colloidal Inks and Temperature‐Sensitive Nanocomposite Films

Abstract With molecularly well‐defined and tailorable 2D structures, covalent organic frameworks (COFs) have emerged as leading material candidates for chemical sensing, storage, separation, and catalysis. In these contexts, the ability to directly and deterministically print COFs into arbitrary geometries will enable rapid optimization and deployment. However, previous attempts to print COFs have been restricted by low spatial resolution and/or post‐deposition polymerization that limits the range of compatible COFs. Here, these limitations are overcome with a pre‐synthesized, solution‐processable colloidal ink that enables aerosol jet printing of COFs with micron‐scale resolution. The ink formulation utilizes the low‐volatility solvent benzonitrile, which is critical to obtaining homogeneous printed COF film morphologies. This ink formulation is also compatible with other colloidal nanomaterials, thus facilitating the integration of COFs into printable nanocomposite films. As a proof‐of‐concept, boronate‐ester COFs are integrated with carbon nanotubes (CNTs) to form printable COF‐CNT nanocomposite films, in which the CNTs enhance charge transport and temperature sensing performance, ultimately resulting in high‐sensitivity temperature sensors that show electrical conductivity variation by 4 orders of magnitude between room temperature and 300 °C. Overall, this work establishes a flexible platform for COF additive manufacturing that will accelerate the incorporation of COFs into technologically significant applications.

2D materials↗

Structural stability of thin overhanging walls during material extrusion additive manufacturing of thermoset-based ink

Recent developments have enabled material extrusion additive manufacturing of thermoset-based composite inks on the large scale. In addition, printing out-of-plane components is of broad interest to the polymer material extrusion community. Here, we address some of the challenges associated with both large-scale and out-of-plane thermoset material extrusion additive manufacturing by studying the height at which thin overhanging walls collapse. Walls at a range of overhang angles were printed until they collapsed. An optical camera captured the profile of each wall throughout the print, allowing the collapse height to be identified and the geometric fidelity to the programmed angle to be evaluated. Using previously measured rheological properties, predictive models were generated to approximate the collapse height and profile of the deflected walls. First, an analytical model was created to predict the height at which the walls would yield. The analytical model assumes the walls exhibit a perfectly linear profile; however, experiments proved this assumption to be false. Therefore, a finite element simulation was developed to account for the elastic deflection that occurs during printing. The finite element simulation predicts both the yield height and the deflected profile after the deposition of each layer. For the properties of the thermoset ink used here, the yield height predicted by the analytical model and finite element simulation are virtually identical. These predictions match experimental data reasonably well, but minor errors are observed. Accounting for the fully plastic moment appears to explain the small mismatch between experimental data and predictions. Additionally, the finite element simulation provides an excellent prediction of the deflected profile before the wall begins to collapse. Finally, by demonstrating that the collapse height and deflected profile of thin overhanging walls can be predicted, this work illustrates how the soft viscoelastic properties of thermoset-based composite inks limit the scale of a key feature required to print some nonplanar components. It also provides a basis to tailor in-process curing systems to suppress deflection and collapse of thin overhanging walls.

36 MATERIALS SCIENCE↗

Combustion-assisted ink-jet printing of nuclear targets

Advances in target fabrication are critical to high-precision measurements in nuclear physics. This work details the preparation of patterned CeO 2 and ThO 2 architectures and thin-film targets via ink-jet deposition of combustible solutions. The produced targets were characterized by scanning electron microscopy (SEM), and by alpha-particle spectroscopy for radioactive targets to determine densities. Ink jet printing of the targets, used both ethanol and 2-methoxyethanol as solvents, with cerium or thorium nitrate as the oxidizer and acetylacetone as the fuel. Additionally, we found that the distance between each droplet dispersion (step size) played the most significant role in determining the final pattern uniformity and thickness. A 50 μm step size leads to relatively thick targets with a density of 350 μg/cm 2 . Significant overlap in droplet sizes leads to a heterogeneous target with an undesirable cracked surface structure. In contrast, 150 μm spacing yields thinner (20 μg/cm 2 ) patterned structures with excellent surface coverage. This method of Ink-jet printing provides a straightforward, scalable, and high-efficiency pathway to prepare custom made, high-quality targets for nuclear physics experiments.

CeO2↗

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↗

Scalable nanomanufacturing of chalcogenide inks: a case study on thermoelectric V–VI nanoplates

Solution-processed semiconducting main-group chalcogenides (MMCs) have attracted increasing research interest for next-generation device technologies owing to their unique nanostructures and superior properties. To achieve the full potential of MMCs, the development of highly universal, scalable, and sustainable synthesis and processing methods of chalcogenide particles is thus becoming progressively more important. Here we studied scalable factors for the synthesis of two-dimensional (2D) V–VI chalcogenide nanoplates (M 2 Q 3 : M = Sb, Bi; Q = Se, Te) and systematically investigated their colloidal behaviour and chemical stability. Based on a solvent engineering technique, we demonstrated scale-up syntheses of MMCs up to a 900% increase of batch size compared with conventional hydrazine-based gram-level syntheses, and such a scalable approach is highly applicable to various binary and ternary MMCs. Furthermore, we studied the stability of printable chalcogenide nanoparticle inks with several formulation factors including solvents, additives, and pH values, resulting in inks with high chemical stability (>4 months). As a proof of concept, we applied our solution-processed chalcogenide particles to multiple additive manufacturing methods, confirming the high printability and processability of MMC inks. Furthermore, the ability to combine the top-down designing freedom of additive manufacturing with bottom-up scalable synthesis of chalcogenide particles promises great opportunities for large-scale design and manufacturing of chalcogenide-based functional devices for broad application.

36 MATERIALS SCIENCE↗