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Development of Stochastic Voronoi Lattice Structures via Two-Photon Polymerization

Low-density polymer foams of varying sizes, shapes, and densities are of specific interest to the inertial confinement fusion (ICF) program and related high-energy density plasma physics research. Historically, these foams are comprised of polystyrene or other low atomic number materials and have densities in the 30 to 300 mg/cm 3 range. However, at the lower end of this density range, these traditional polymer foams become fragile and difficult to cast and machine into the geometries needed. Recently, the need by experimentalists for materials with densities below 30 mg/cm 3 has increased. To address these needs, we are developing three-dimensional (3-D) printing techniques to create high-precision, low-density, and repeatable complex lattice structures. Using two-photon polymerization 3-D printing, we recently developed the first 5 mg/cm3 low-density lattice structure having an annular hemispherical shape. These microscale to mesoscale structures were modeled and designed using the nTopology software, specifically utilizing the "Voronoi volume lattice" and "random points in body" option blocks. All printing operations were performed using the Nanoscribe Photonic Professional GT instrument. Characterization of these 3-D structures was conducted using various microscopic and X-ray tomographic imaging techniques. Furthermore, overall printed part sizes ranged from 1 to 5 mm in diameter and were composed of lattice ligaments having thicknesses in the 3- to 5-µm range. These structures have been incorporated into ICF targets recently shot on both the University of Rochester’s Laboratory of Laser Energetics Omega laser and the National Ignition Facility.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Shock compression of a low-density carbon foam

Porous polymer foams are found in numerous applications where they may be subjected to dynamic compression. The shockwave properties of polymer foams have several features that make shock Hugoniot measurements and interpretation challenging. Here, we present a comparison of dynamic X-ray phase contrast imaging and traditional optical velocimetry approaches to measuring the shocked states for a low-density carbon foam. Overall, dynamic X-ray phase contrast imaging was found to reduce errors associated with the measured Hugoniot states. In this study, the foam exhibits anomalous compression as expected due to its high initial porosity arising from shock heating.

36 MATERIALS SCIENCE↗

Physics of interplanetary dust capture via impact into organic polymer foams

The physics of hypervelocity impacts into foams is of interest because of the possible application to interplanetary dust particle (IDP) capture by spacecraft. We present a model for the phenomena occurring in such impacts into low-density organic polymer foams. Particles smaller than foam cells behave as if the foam is a series of solid slabs and are fragmented and, at higher velocities, thermally altered. Particles much larger than the foam cells behave as if the foam were a continuum, allowing the use of a continuum mechanics model to describe the effects of drag and ablation. Fragmentation is expected to be a major process, especially for aggregates of small grains. Calculations based on these arguments accurately predict experimental data and, for hypothetical IDPs, indicate that recovery of organic materials will be low for encounter velocities greater than 5 km/s. For an organic particle 100 micrometers in diameter, approx. 35% of the original mass would be collected in an impact at 5 km/s, dropping to approx. 10% at 10 km/s and approx. 0% at 15 km/s. For the same velocities the recovery ratios for troilite (FeS) are approx. 95%, 65%, and 50%, and for olivine (Mg2SiO4) they are approx. 98%, 80%, and 65%, demonstrating that inorganic materials are much more easily collected. The density of the collector material has only a second-order effect, changing the recovered mass by less than 10% of the original mass.

Anderson, William W.↗

Determining the nanostructure of polymer foams using 3D ptycho-tomography for inertial fusion energy applications

Polymer foams play a critical role in contemporary inertial fusion energy (IFE) target designs by enhancing energy yield and optimizing implosion dynamics. However, the lack of high-resolution characterization of the nanostructure of these foams restricts progress in fusion science. In this work, we demonstrate the first high-resolution three-dimensional (3D) reconstruction of a low-density, Si-doped polymer foam fabricated via two-photon polymerization, using ptychographic x-ray computed tomography (PXCT) at an x-ray free electron laser (XFEL). This imaging method reconstructs two-dimensional (2D) attenuation and phase information at multiple sample angles that are combined into a 3D density map used to extract local mass density and determine structural dimensions. We achieve a 2D spatial resolution of 19 ± 3 nm on a high-contrast Ronchi pattern target and 78.7 ± 3 nm for low-contrast polymer foams, marking a significant advancement for XFEL-based ptychography of low-density materials. Furthermore, our experimental results reveal an average foam strut thickness of 1.17 ± 0.4 μm, consistent with fabrication expectations, and a reconstructed average mass density of 0.35 g/cc, aligning closely with the predicted density of 0.29 g/cc. These findings provide important insights for improving foam design and refining radiation hydrodynamics modeling in future IFE experiments. Our study establishes PXCT at an XFEL as a powerful tool for high-resolution characterization of fusion-relevant materials, paving the way for enhanced target performance in IFE research.

Hancock, Levi [Colorado State Univ., Fort Collins,↗

Lignin-Based Low-Density Rigid Polyurethane/Polyisocyanurate Foams

In this paper, unmodified kraft softwood lignin was utilized to fully replace the petroleum-based polyol for the first time in low-density rigid polyurethane/polyisocyanurate (PUR/PIR) foam. The effects of different lignin incorporation levels (0, 25, 50, 75, and 100%) on foam properties were investigated by measuring foam’s reactivity, polyol viscosity (using a rheometer), apparent density, compression strength, closed cell content (using a gas pycnometer), thermal conductivity, fire resistance, and morphology (observed through SEM). All formulated lignin-based foams met the ASTM minimum requirements for type 1 rigid insulation foams. Remarkably, the foam made by replacing 100% of the petrochemical polyol with the commercially available kraft lignin demonstrated outstanding fire resistance performance, reducing the burn length by 127%.

09 BIOMASS FUELS↗

Functional Photoresists for Energy Applications. Final Report

Monolithic ultralow-density porous bulk materials have recently attracted much interest due to many emerging applications in the areas of catalysis, energy storage and conversion, and thermal insulation. They are also important components of high energy density (HED) and inertial confinement fusion (ICF) targets. However, despite tremendous progress that has been made in the synthesis of porous materials, deterministic and independent control over microscopic architecture, density and composition remain key issues, and their integration in high precision devices requires cost and time-intensive mechanical machining that not only reduces reproducibility by generating debris but also limits the complexity of the 3D shapes that can be realized. In this project, we overcame these limitations by developing a universal templating capability that provides deterministic and independent control over density, composition, architecture, and macroscopic sample shape. This was achieved by developing the technology to 1) 3D print ultrahigh resolution, ultra-high precision polymeric micro-lattice templates, 2) coat these templates with the desired materials, and 3) removing the template (Fig. 1a). Atomic layer deposition (ALD) provides the atomic scale coating thickness accuracy required for precisely controlling density. While this templating approach had been demonstrated in prior work, limitations in suitable photoresists, 3D print technologies, print design, and template removal techniques did not allow the fabrication of millimeter-sized high-precision parts with sub-micron resolution. To enable this technology, we developed 1) two-photon polymerization (TPP) print designs that enable the fabrication of millimeter-sized, mechanically robust polymeric templates with sub-micron resolution and 2) a continuum level TPP printing simulation capability for additional print design guidance; 3) atomistic models to study photoresist polymerization kinetics and network topography, 4) refractive index matched polymeric and preceramic TPP photoresists, and 5) functional TPP photoresists including porous voxel structures and self-immolative polymer photoresist chemistries; and 6) damage free template removal techniques that enable the fabrication of defect-free high-precision low-density foam components. We also developed a templating approach for pure carbon microlattices with a unique tube-in-tube ligament morphology. As a test platform, we pursued the fabrication of foam liners that promise to further increase the neutron yield in indirect drive ICF experiments by improving implosion symmetry control and coupling between the laser and the deuterium-tritium fuel. This application requires fabrication and integration of a ultra-high precision, millimeter-sized, thin-walled (200-400 micrometer thick), low-density (10-30 mg/cc), high atomic number (high Z) cylindrical foam tube into the gold hohlraum of an indirect drive ICF target (Fig. 1b). While our hohlraum liner test case will mainly find application in HED and ICF experiments, the underlying science will also directly apply to previously developed nanoparticle and additive manufacturing technologies and will advance those techniques as well.

36 MATERIALS SCIENCE↗

Preparation of Macroscopic Low-Density Gold Foams with Good Machinability

Uniform, macroscopic monoliths (ranging from a few millimeters to a centimeter) of low-density gold foams with ~95% porosity and ~10-μm-diameter pores were prepared by the casting of gold-coated polystyrene core-shell particles followed by the thermal removal of the polymer core. The Au foams were composed of unique hollow gold spheres and showed superior mechanical integrity and resilience compared to the foams we previously reported. Highly efficient seeding and electroless gold-plating methods in this study caused a significant morphological transition in the gold coatings from coarse particles to fine particles, and finally, to a continuous layer. A modified, scalable casting approach to form large uniform monoliths (up to ~1-cm diameter) and a gentle baking condition to minimize undesirable densification of the final foams enabled us to develop a simple, efficient synthetic route to nanostructured macroscopic low-density gold foams. To demonstrate the improved mechanical stability and machinability, a representative monolithic Au foam (~0.9 g/cm 3 ) was carefully cut into the hollow cylinder of gold foams by a series of machining and processing steps. Finally, we tried to understand the unique mechanical behaviors and properties of this gold foam by nanoindentation measurement.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Preparation of Mechanically Robust, Macroscopic Low-Density Gold Foams by Highly Efficient Electroless Gold Plating

Mechanically robust, macroscopic-sized low-density gold foams with unique morphology of hollow gold shells were prepared by the synthesis of gold-coated polystyrene coreshell particles followed by thermal removal of the polymer core. Here, we reported a simple, highly efficient electroless gold plating procedure to form ultrathin, conformal gold coatings on the surface of polystyrene particles. A modified, scalable casting approach to form uniform, large monoliths (up to 1 cm diameter) and a baking condition to minimize undesirable densification of final foams were also developed. To demonstrate the mechanical stability and integrity of the Au foams, a representative monolithic sample (~0.9 g/ cm3 ) was successfully cut and shaped into a gold foam “washer” by a series of precision machining and processing. A depth-sensing indentation test (nanoindentation) as well as characterizations on other useful properties such as surface areas and electrical conductivity of the Au foams were carried out to understand the mechanical behavior and potential applicability.

Electroless Gold Plating↗

Nonlinear Spring Finite Elements for Predicting Mode I-Dominated Delamination Growth in Laminated Structure with Through-Thickness reinforcement

One particular concern of polymer matrix composite laminates is the relatively low resistance to delamination cracking, in particular when the dominant type of failure is mode I opening. One method proposed for alleviating this problem involves the insertion pultruded carbon pins through the laminate thickness. The pins, known as z-pins, are inserted into the prepreg laminate using an ultrasonic hammer prior to the curing process, resulting in a field of pins embedded normal to the laminate plane as illustrated in Figure. 1. Pin diameters range between 0.28-mm to 0.5-mm and standard areal densities range from 0.5% to 4%. The z-pins are provided by the manufacturer, Aztex(Registered TradeMark) , in a low-density foam preform, which acts to stabilize orientation of the pins during the insertion process [1-3]. Typical pin materials include boron and carbon fibers embedded in a polymer matrix. A number of methods have been developed for predicting delamination growth in laminates reinforced with z-pins. During a study on the effect of z-pin reinforcement on mode I delamination resistance, finite element analyses of z-pin reinforced double cantilever beam (DCB) specimens were performed by Cartie and Partridge [4]. The z-pin bridging stresses were modeled by applying equivalent forces at the pin locations. Single z-pin pull-out tests were performed to characterize the traction law of the pins under mode I loading conditions. Analytical solutions for delamination growth in z-pin reinforced DCB specimens were independently derived by Robinson and Das [5] and Ratcliffe and O'Brien [6]. In the former case, pin bridging stresses were modeled using a distributed load and in the latter example the bridging stresses were discretely modeled by way of grounded springs. Additionally, Robinson and Das developed a data reduction strategy for calculating mode I fracture toughness, G(sub Ic), from a z-pin reinforced DCB specimen test [5]. In both cases a traction law similar to that adopted by Cartie and Partridge was used to represent z-pin failure under mode I loading conditions. In the current work spring elements available in most commercial finite element codes were used to model z-pins. The traction law used in previous analyses [4-6] was employed to represent z-pin damage. This method is intended for and is limited to simulating z-pins in composite laminate structure containing mode I-dominated delamination cracking. The current technique differs from previous analyses in that spring finite elements (available in commercial codes) are employed for simulating zpins, reducing the complexity of the analysis construction process. Furthermore, the analysis method can be applied to general structure that experiences mode I-dominated delamination cracking, in contrast to existing analytical solutions that are only applicable to coupon DCB specimens.

Ratcliffe, James G.↗

Circular Reprocessing of Thermoset Polyurethane Foams

Thermoset polyurethane (PU) foams are widely used in industrial applications, but they cannot be recycled by conventional melt reprocessing because of their cross-linked structures. The introduction of carbamate exchange catalysts converts thermoset PU into covalent adaptable networks (CANs), which are amenable to reprocessing at elevated temperatures. However, this approach has produced solid PU films, which have fewer uses and lower commercial demand. In this work, simultaneous reprocessing and refoaming of thermoset PU foams is demonstrated by leveraging the melt-processability of PU CANs and allowing cell growth by gas generation in a twin-screw extruder. The optimal operating temperature of the refoaming process is determined through chemical, thermal, and structural analysis of PU foam extrudates. The foam-to-foam extrusion process produces controllable, continuous, and uniform foam structures, as characterized by cell diameter and cell number density. Low-density PU foams are obtained through a process simulating injection molding. The compression properties of reprocessed PU foam are compared with as-synthesized PU foam to demonstrate efficacy of the refoaming processes. These results demonstrate that PU foams can be prepared through recycling while maintaining microstructural and chemical integrity. In the future, this strategy may be applied to thermoset PU foams of various chemical compositions and shows promise for scalability.

36 MATERIALS SCIENCE↗

The intact capture of hypervelocity dust particles using underdense foams

The impact of a hypervelocity projectile (greater than 3 km/s) is a process that subjects both the impactor and the impacted material to a large transient pressure distribution. The resultant stresses cause a large degree of fragmentation, melting, vaporization, and ionization (for normal densities). The pressure regime magnitude, however, is directly related to the density relationship between the projectile and target materials. As a consequence, a high-density impactor on a low-density target will experience the lowest level of damage. Historically, there have been three different approaches toward achieving the lowest possible target density. The first employs a projectile impinging on a foil or film of moderate density, but whose thickness is much less than the particle diameter. This results in the particle experiencing a pressure transient with both a short duration and a greatly reduced destructive effect. A succession of these films, spaced to allow nondestructive energy dissipation between impacts, will reduce the impactor's kinetic energy without allowing its internal energy to rise to the point where destruction of the projectile mass will occur. An added advantage to this method is that it yields the possibility of regions within the captured particle where a minimum of thermal modification has taken place. Polymer foams have been employed as the primary method of capturing particles with minimum degradation. The manufacture of extremely low bulk density materials is usually achieved by the introduction of voids into the material base. It must be noted, however, that a foam structure only has a true bulk density of the mixture at sizes much larger than the cell size, since for impact processes this is of paramount importance. The scale at which the bulk density must still be close to that of the mixture is approximately equal to the impactor. When this density criterion is met, shock pressures during impact are minimized, which in turn maximizes the probability of survival for the impacting particle. The primary objectives of the experiment are to (1) Examine the morphology of primary and secondary hypervelocity impact craters. Primary attention will be paid to craters caused by ejecta during hypervelocity impacts of different substrates. (2) Determine the size distribution of ejecta by means of witness plates and collect fragments of ejecta from craters by means of momentum-sensitive mcropore foam. (3) Assess the directionality of the flux by means of penetration-hole alignment of thin films placed above the cells. (4) Capture intact the particles that perforated the thin film and entered the cell. Capture media consisted of both previously flight-tested micropore foams and aerogel. The foams had different latent heats of fusion and, accordingly, will capture particles over a range of momenta. Aerogel was incorporated into the cells to determine the minimum diameter than can be captured intact.

Maag, Carl R.↗