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Porous Microstructure Analysis (PuMA) software

The Porous Microstructure Analysis (PuMA) software was developed to provide a robust and efficient framework for computing material properties based on their microstructures. The development was motivated by advancements in X-ray microtomography, an imaging technology that can resolve the structure of a material at a sub-micron scale, in 3D and even in 4D (over time). PuMA provides the capability of computing a comprehensive spectrum of properties, from the most fundamental geometric features of a microstructure, to advanced anisotropic thermo-elastic properties. In addition, the software can generate artificial microstructures, ranging from simple analytical shapes to complex fibrous woven and non- woven geometries, which can be used in performance optimization studies. This presentation will highlight many of the capabilities of the recent open-source release.

microtomography↗

DOE OSTI2024

A Bulk versus Nanoscale Hydrogen Storage Paradox Revealed by Material-System Co-Design

Metal hydrides are serious contenders for materials-based hydrogen storage to overcome constraints associated with compressed or liquefied H 2 . Their ultimate performance is usually evaluated using intrinsic material properties without considering a systems design perspective. An illustrative case with startling implications is (LiNH 2 +2LiH). Using models that simulate the storage system and associated fuel cell of a light-duty vehicle (LDV), the performance of the bulk hydrides is compared with a nanoscaled version in porous carbon (PC), (LiNH 2 +2LiH)@(6-nm PC). Using experimental material properties, the simulations show that (LiNH 2 +2LiH)@(6-nm PC) counterintuitively has higher usable gravimetric and volumetric capacities than the bulk counterpart on a system basis despite having lower capacities on a materials-only basis. Nanoscaling increases the thermal conductivity and lowers the desorption enthalpy, which consequently increases heat management efficiency. In a simulated drive cycle for fuel cell-powered LDV, the fuel cell is inoperable using bulk (LiNH 2 +2LiH) as the storage material but completes the drive cycle using the nanoscale material. Further, these results challenge the notion that nanoscaling incurs mass and volume penalties. Instead, the synergistic nanoporous host-hydride interaction can favorably modulate chemical and heat transfer properties. Moreover, a co-design approach considering application-specific tradeoffs is essential to accurately assess a material's potential for real-world hydrogen storage.

08 HYDROGEN↗

DOE OSTI2023

Towards the design of nature-inspired materials: Impact of complex pore morphologies via higher-order homogenization

Even though the development of novel materials that mimic nature is widely used in a variety of engineering and scientific fields, the relationship between effective material properties and underlying, often complex pore morphology is still not fully understood. To address this knowledge gap and accelerate the development of novel nature-inspired materials, this paper adopts a higher-order asymptotic homogenization method to numerically investigate the effect of complex micropore morphology on the effective mechanical properties of a porous system. Specifically, we create unique pore morphologies with varying levels of complexity that serve as a more realistic representation of natural materials. Here, we then use the second-order homogenization method to capture the role of pore size, shape, orientation, and distribution on effective properties. By creating different pore morphologies, we systematically studied the relationship between morphology and effective mechanical properties. The results highlight the necessity of higher-order parameters to fully capture the role of realistic pore morphologies on effective mechanical properties and provide a path forward in the design of nature-inspired materials.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Scaffolding matrix with internal nanoparticles

A battery electrode composition is provided comprising composite particles, with each composite particle comprising active material and a scaffolding matrix. The active material is provided to store and release ions during battery operation. For certain active materials of interest, the storing and releasing of the ions causes a substantial change in volume of the active material. The scaffolding matrix is provided as a porous, electrically-conductive scaffolding matrix within which the active material is disposed. In this way, the scaffolding matrix structurally supports the active material, electrically interconnects the active material, and accommodates the changes in volume of the active material.

Yushin, Gleb↗

DOE OSTI2022

Scaffolding matrix with internal nanoparticles

25 ENERGY STORAGE↗

DOE OSTI2024

Scaffolding matrix with internal nanoparticles

Yushin, Gleb↗

NASA NTRS1989

Ceramic heat pipe wick

A wick for use in a capillary loop pump heat pipe is disclosed. The wick material is an essentially uniformly porous, permeable, open-cell, silicon dioxide/aluminum oxide inorganic ceramic foam having a silica fiber ratio, by weight, of about 78 to 22, respectively, a density of 6 lbs/cu ft, and an average pore size of less than 5 microns. A representative material having these characteristics is Lockheed Missile and Space Company, Inc.'s HTP 6-22. This material is fully compatible with the freons and anhydrous ammonia and allows for the use of these very efficient working fluids, and others, in capillary loops.

Seidenberg, Benjamin↗

DOE OSTI2024

Upcycling Linear Low-Density Polyethylene Waste into Graphene for High Mass Loading Supercapacitors

Upcycling plastic into advanced carbons, such as graphene and porous carbon, offers attractive options to manage waste streams by converting the plastic into carbon electrode materials for energy storage devices. Linear low density polyethylene (LLDPE) is firstly bulk-oxidized with a facile and scalable method and then carbonized and catalyticlly graphenized into porous graphene materials. The LLDPE derived graphene (LLDPE-G) has a BET specific surface area up to 1800 m2/g and Raman ID/IG ratio of 0.85. When used as electrode material for symmetric supercapacitor, LLDPE-G possesses outstanding specific capacitance and excellent areal capacitance. Moreover, LLDPE-G exhibits exceptional cycling stability with capacitance retention of 95.8% after 100,000 cycles. Last but not least, KCl is recycled and reused over 3 cycles with material quality and electrocapacitive performance of LLDPE-G retained and verified after each cycle.

Gao, Yuan↗

DOE OSTI2022

Evaluating solvothermal and mechanochemical routes towards the metal–organic framework Mg 2 ( m -dobdc)

Metal–organic frameworks bearing coordinatively unsaturated Mg(II) sites are promising materials for gas storage, chemical separations, and drug delivery due to their low molecular weights and lack of toxicity. Furthermore, there remains a limited number of such MOFs reported in the literature. Herein, we investigate the gas sorption properties of the understudied framework Mg 2 (m-dobdc) (dobdc 4– = 4,6-dioxido-1,3-benzenedicarboxylate) synthesized under both solvothermal and mechanochemical conditions. Both materials are found to be permanently porous, as confirmed by 77 K N 2 adsorption measurements. In particular, Mg 2 (m-dobdc) synthesized under mechanochemical conditions using exogenous organic base displays one of the highest capacities reported to date (6.14 mmol g –1 ) for CO 2 capture in a porous solid under simulated coal flue gas conditions (150 mbar, 40 °C). As such, mechanochemically synthesized Mg 2 (m-dobdc) represents a promising new framework for applications requiring high gas adsorption capacities in a porous solid.

36 MATERIALS SCIENCE↗

NASA NTRS1980

Chelate-modified polymers for atmospheric gas chromatography

Chromatographic materials were developed to serve as the stationary phase of columns used in the separation of atmospheric gases. These materials consist of a crosslinked porous polymer matrix, e.g., a divinylbenzene polymer, into which has been embedded an inorganic complexed ion such as N,N'-ethylene-bis-(acetylacetoniminato)-cobalt (2). Organic nitrogenous bases, such as pyridine, may be incorporated into the chelate polymer complexes to increase their chromatographic utility. With such materials, the process of gas chromatography is greatly simplified, especially in terms of time and quantity of material needed for a gas separation.

Christensen, W. W.↗

DOE OSTI2021

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↗

DOE OSTI2022

Simulating the non-monotonic strain response of nanoporous multiferroic composites under electric field control

In this work, we simulate and analyze the mechanical response of a class of multiferroic materials consisting of a templated porous nanostructure made out of cobalt ferrite (CFO) partially filled by atomic layer deposition (ALD) with a ferroelectric phase of lead zirconate titanate (PZT). The strain in the device is measured when an electric field is applied for varying ALD thicknesses, displaying a non-monotonic dependence with a maximum strain achieved for a coating thickness of 3 nm. To understand this behavior, we apply finite element modeling to the smallest repeatable unit of the nanoporous template and simulate the mechanical response as a function of PZT coating thickness. We find that this non-monotonic response is caused by the interplay between two driving forces opposing one another. First, increased porosity works toward increasing the strain due to a reduced system stiffness. Second, decreased porosity involves a larger mass fraction of PZT, which drives the electro-mechanical response of the structure, thus leading to a larger strain. The balance between these two driving forces is controlled by the shear coupling at the CFO/PZT interface and the effective PZT cross section along the direction of the applied electric field. Here, our numerical results show that considering a nonlinear piezoelectric response for PZT leads to an improved agreement with the experimental data, consistent with ex situ poling of the nanostructure prior to magnetic measurements.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2021

Engineering Permanent Porosity into Liquids

The possibility of engineering well-defined pores into liquid materials is fascinating from both a conceptual and an applications point of view. Although the concept of porous liquids was proposed in 2007, these materials had remained hypothetical due to the technical challenges associated with their synthesis. Over the past five years, however, reports of the successful construction of porous liquids based on existing porous scaffolds, such as coordination cages, organic cages, metal–organic frameworks, porous carbons, zeolites, and porous polymers, have started to emerge. Here, the focus is on these early reports of porous liquids as prototypes in the field, classified according to the previously defined types of porous liquids. Particular attention will be paid to design strategies and structure–property relationships. Porous liquids have already exhibited promising applications in gas storage, transportation, and chemical separations. Furthermore, they show great potential for use in the chemical industry. The challenges of preparation, scale-up, volatility, thermal and chemical stability, and competition with porous solids will also be discussed.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Bifunctional Heterometallic Metal-Organic Frameworks for Solvent-Free Heterogeneous Cascade Catalysis

A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.

36 MATERIALS SCIENCE↗

DOE OSTI2024

One-Pot Self-Assembly of Sequence-Controlled Mesoporous Heterostructures via Structure-Directing Agents

Multimaterial heterostructures have led to characteristics surpassing the individual components. Nature controls the architecture and placement of multiple materials through biomineralization of nanoparticles (NPs); however, synthetic heterostructure formation remains limited and generally departs from the elegance of self-assembly. Here, in this study, a class of block polymer structure-directing agents (SDAs) are developed containing repeat units capable of persistent (covalent) NP interactions that enable the direct fabrication of nanoscale porous heterostructures, where a single material is localized at the pore surface as a continuous layer. This SDA binding motif (design rule 1) enables sequence-controlled heterostructures, where the composition profile and interfaces correspond to the synthetic addition order. This approach is generalized with 5 material sequences using an SDA with only persistent SDA-NP interactions (“P-NP 1 –NP 2 ”; NP i = TiO 2 , Nb 2 O 5 , ZrO 2 ). Expanding these polymer SDA design guidelines, it is shown that the combination of both persistent and dynamic (noncovalent) SDA-NP interactions (“PD-NP 1 –NP 2 ”) improves the production of uniform interconnected porosity (design rule 2). The resulting competitive binding between two segments of the SDA (P- vs D-) requires additional time for the first NP type (NP 1 ) to reach and covalently attach to the SDA (design rule 3). The combination of these three design rules enables the direct self-assembly of heterostructures that localize a single material at the pore surface while preserving continuous porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2015

Method for Producing Launch/Landing Pads and Structures Project

Current plans for deep space exploration include building landing-launch pads capable of withstanding the rocket blast of much larger spacecraft that that of the Apollo days. The proposed concept will develop lightweight launch and landing pad materials from in-situ materials, utilizing regolith to produce controllable porous cast metallic foam brickstiles shapes. These shapes can be utilized to lay a landing launch platform, as a construction material or as more complex parts of mechanical assemblies.

Technology Portfolio System↗

NASA NTRS2015

Electrochemical Cell with Improved Water or Gas Management

An electrochemical cell having a water/gas porous separator prepared from a polymeric material and one or more conductive cell components that pass through, or are located in close proximity to, the water/gas porous separator, is provided. The inventive cell provides a high level of in-cell electrical conductivity.

Smith, William F.↗

DOE OSTI2024

Methods of fabricating porous ceramic electrodes for solid state battery applications

Compositions and methods for the fabrication of electrode and porous lithium-garnet electrolyte scaffolds for use in solid state batteries and other devices are provided. The methods produce porous structures using phase inversion or high shear compaction processes to fabricate a solid-state battery electrode material from LLZO electrolytes. Engineered electrode structures with a porous scaffold of solid electrolyte material provide lower interfacial resistances and a mechanical support for a thin solid electrode layer improving performance.

Tucker, Michael↗