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The hydrogen uptake kinetics of 1,4-bis(phenylethynyl)benzene, or DEB, mixed with palladium (Pd) on activated carbon in a rubber matrix coating on top of a porous silicone foam substrate are investigated. First, isothermal isobaric hydrogenation experiments were performed under different temperatures and H2 pressures to extract the uptake kinetics. The H2 uptake models based on the measured kinetic parameters were then employed to investigate/simulate the performance of the getter under dynamic application environments. The actual hydrogenation characteristics in this type of getter are multifaceted and involve actual H2 concentration in the getter matrix, micrometer-scale diffusion of atomic hydrogen away from Pd sites, precipitation of hydrogenated DEB crystals at the coating surfaces, and mobility of fresh DEB molecules. The kinetic analysis/modeling methodology described in this report can serve as a template for other gas-solid reactions as well. Besides possessing a good hydrogen capacity and excellent performance, this type of rubberized getter also offers some unique advantages over traditional solid getter: flexible structure and protection of the Pd catalyst from exposure to the environment.

Filled silicone elastomers, an essential component in many technological applications, are often subjected to controlled or unintended radiation for a variety of reasons. Radiation exposure can lead to permanent mechanical and structural changes in the material, which is manifested as altered mechanical response, and in some cases, a permanent set. For unfilled elastomers, network theories developed and refined over decades can explain these effects in terms of chain-scission and cross-link formation and a hypothesis involving independent networks formed at different strain levels of the material. Here, we expose a filled silicone rubber to gamma radiation while being under finite elongational strain and show that the observed mechanical and structural changes can be quantitatively modeled within the same theoretical framework developed for unfilled elastomers as long as nuances associated with the Mullins effect are accounted for in a consistent manner. In this work, we employ Ogden's incompressible hyperelastic model within the framework of Tobolsky's two-network scheme to describe the observed permanent set and mechanical modulus changes as a function of radiation dosage. In the process, we conclude that gamma radiation induces both direct cross-linking at chain crossings (H-links) and main-chain-scission followed by cross-linking (Y-links). We provide an estimate of the ratio of chain-scission to cross-linking rates, which is in reasonable agreement with previous experimental estimate from Charlesby-Pinner analysis. We use density functional theory (DFT)-based quantum mechanical calculations to explore the stability of -Si and -SiO radicals that form upon a radiation-induced chain-scission event, which sheds light on the relative rates of Y-linking and H-linking processes.

Direct ink writing of silicone elastomers enables printing with precise control of porosity and mechanical properties of ordered cellular solids, suitable for shock absorption and stress mitigation applications. With the ability to manipulate structure and feedstock stiffness, the design space becomes challenging to parse to obtain a solution producing a desired mechanical response. Here, we derive an analytical design approach for a specific architecture. Results from finite element simulations and quasi-static mechanical tests of two different parallel strand architectures were analyzed to understand the structure-property relationships under uniaxial compression. Combining effective stiffness-density scaling with least squares optimization of the stress responses yielded general response curves parameterized by resin modulus and strand spacing. An analytical expression of these curves serves as a reduced order model, which, when optimized, provides a rapid design capability for filament-based 3D printed structures. As a demonstration, the optimal design of a face-centered tetragonal architecture is computed that satisfies prescribed minimum and maximum load constraints.

Traditional open or closed-cell stochastic elastomeric foams have wide-ranging applications in numerous industries: from thermal insulation, shock absorbing/gap-filling support cushions, packaging, to light-weight structural and positional components. Recent developments in 3D printing technologies by direct ink-write have opened the possibility of replacing stochastic foam parts by more controlled printed micro-structures with superior stress-distribution and longer functional life. For successful deployment as mechanical support or structural components, it is crucial to characterize the response of such printed materials to long-term external loads in terms of stress-strain behavior evolution and in terms of irreversible structural and load-bearing capacity changes over time. To this end, here we report a thermal-age-aware constitutive model for a 3D printed close-packed foam structure under compression. The model is based on the Ogden hyperfoam strain-energy functional within the framework of Tobolsky two-network scheme. It accurately describes experimentally measured stress-strain response, compression set, and load retention for various aging times and temperatures. Through the technique of time-temperature-superposition the model enables the prediction of long-term changes along with the quantification of uncertainty stemming from sample-to-sample variation and measurement noise. All aging parameters appear to possess the same Arrhenius activation barrier, which suggests a single dominant aging mechanism at the molecular/network level.

Shape memory polymer (SMP) foams have been developed for use in neurovascular occlusion applications. These materials are predominantly polyurethanes that are known for their biocompatibility and tunable properties. However, these polymers inherently lack X-ray visibility, which is a significant challenge for their use as implantable materials. Herein, low density, highly porous shape memory polyurethane foams were developed with tungsten nanoparticles dispersed into the foam matrix, at increasing concentrations, to serve as a radiopaque agent. Utilizing X-ray fluoroscopy sufficient visibility of the foams at small geometries was observed. Thermal characterization of the foams indicated altered thermal response and delayed foam actuation with increasing nanoparticle loading (because of restricted network mobility). Mechanical testing indicated decreased toughness and strength for higher loading because of disruption of the SMP matrix. Overall, filler addition imparted x-ray visibility to the SMP foams and allowed for tuned control of the transition temperature and actuation kinetics for the material.

Shape memory polymer (SMP) foams have been developed for use in neurovascular occlusion applications. These materials are predominantly polyurethanes that are known for their biocompatibility and tunable properties. However, these polymers inherently lack X-ray visibility, which is a significant challenge for their use as implantable materials. Herein, low density, highly porous shape memory polyurethane foams were developed with tungsten nanoparticles dispersed into the foam matrix, at increasing concentrations, to serve as a radiopaque agent. Utilizing X-ray fluoroscopy sufficient visibility of the foams at small geometries was observed. Thermal characterization of the foams indicated altered thermal response and delayed foam actuation with increasing nanoparticle loading (because of restricted network mobility). Mechanical testing indicated decreased toughness and strength for higher loading because of disruption of the SMP matrix. Overall, filler addition imparted x-ray visibility to the SMP foams and allowed for tuned control of the transition temperature and actuation kinetics for the material. Copyright © 2015 John Wiley & Sons, Ltd.

Polyurethane shape memory polymers (SMPs) with tunable thermomechanical properties and advanced processing capabilities are synthesized, characterized, and implemented in the design of a microactuator medical device prototype. The ability to manipulate glass transition temperature (Tg ) and crosslink density in low-molecular weight aliphatic thermoplastic polyurethane SMPs is demonstrated using a synthetic approach that employs UV catalyzed thiol-ene "click" reactions to achieve postpolymerization crosslinking. Polyurethanes containing varying C=C functionalization are synthesized, solution blended with polythiol crosslinking agents and photoinitiator and subjected to UV irradiation, and the effects of number of synthetic parameters on crosslink density are reported. Thermomechanical properties are highly tunable, including glass transitions tailorable between 30 and 105 °C and rubbery moduli tailorable between 0.4 and 20 MPa. This new SMP system exhibits high toughness for many formulations, especially in the case of low crosslink density materials, for which toughness exceeds 90 MJ m(-3) at select straining temperatures. To demonstrate the advanced processing capability and synthetic versatility of this new SMP system, a laser-actuated SMP microgripper device for minimally invasive delivery of endovascular devices is fabricated, shown to exhibit an average gripping force of 1.43 ± 0.37 N and successfully deployed in an in vitro experimental setup under simulated physiological conditions.

Cellular solids or foams are a very important class of materials with diverse applications ranging from thermal insulation and shock absorbing support cushions, to light-weight structural and floatation components, and constitute crucial components in a large number of industries including automotive, aerospace, electronics, marine, biomedical, packaging, and defense. In many of these applications the foam material is subjected to long periods of continuous stress, which can, over time, lead to a permanent change in structure and a degradation in performance. In this report we summarize our modeling efforts to date on polysiloxane foam materials that form an important component in our systems. Aging of the materials was characterized by two measured quantities, i.e., compression set and load retention. Results of accelerated aging experiments were analyzed by an automated time-temperaturesuperposition (TTS) approach, which creates a master curve that can be used for long-term predictions (over decades) under ambient conditions. When comparing such master curves for traditional (stochastic) foams with those for recently 3D-printed (i.e., additively manufactured, or AM) foams, it became clear that AM foams have superior aging behavior. To gain deeper understanding, we imaged the microstructure of both foams using X-ray computed tomography, and performed finite-element analysis of the mechanicalmore » response within these microstructures. This indicates a wider stress variation in the stochastic foam with points of more extreme local stress as compared to the 3D printed material.« less

Shape memory polymers (SMPs) are attractive materials due to their unique mechanical properties, including high deformation capacity and shape recovery. SMPs are easier to process, lightweight, and inexpensive compared to their metallic counterparts, shape memory alloys. However, SMPs are limited to relatively small form factors due to their low recovery stresses. Lightweight, micro-architected composite SMPs may overcome these size limitations and offer the ability to combine functional properties (e.g., electrical conductivity) with shape memory behavior. Fabrication of 3D SMP thermoset structures via traditional manufacturing methods is challenging, especially for designs that are composed of multiple materials within porous microarchitectures designed for specific shape change strategies, e.g. sequential shape recovery. We report thermoset SMP composite inks containing some materials from renewable resources that can be 3D printed into complex, multi-material architectures that exhibit programmable shape changes with temperature and time. Through addition of fiber-based fillers, we demonstrate printing of electrically conductive SMPs where multiple shape states may induce functional changes in a device and that shape changes can be actuated via heating of printed composites. The ability of SMPs to recover their original shapes will be advantageous for a broad range of applications, including medical, aerospace, and robotic devices.

Scientific Reports 6: Article number: 24871; Published online: 27 April 2016; Updated 25 May 2016 The Acknowledgements section in this Article is incomplete. “We would like to sincerely thank Dr. Jim Schneider of National Security Campus, MO (formerly Kansas City Plant) for giving us access to the results of their load retention study on the stochastic foam material.

3D printing of polymeric foams by direct-ink-write is a recent technological breakthrough that enables the creation of versatile compressible solids with programmable microstructure, customizable shapes, and tunable mechanical response including negative elastic modulus. However, in many applications the success of these 3D printed materials as a viable replacement for traditional stochastic foams critically depends on their mechanical performance and micro-architectural stability while deployed under long-term mechanical strain. To predict the long-term performance of the two types of foams we employed multi-year-long accelerated aging studies under compressive strain followed by a time-temperature-superposition analysis using a minimum-arc-length-based algorithm. The resulting master curves predict superior long-term performance of the 3D printed foam in terms of two different metrics, i.e., compression set and load retention. To gain deeper understanding, we imaged the microstructure of both foams using X-ray computed tomography, and performed finite-element analysis of the mechanical response within these microstructures. This indicates a wider stress variation in the stochastic foam with points of more extreme local stress as compared to the 3D printed material, which might explain the latter’s improved long-term stability and mechanical performance.

Polyurethane shape memory polymers (SMPs) have found a variety of uses in the medical industry in the form of self-tightening sutures, suture anchors, ligament fixation devices, vascular stents, and thrombectomy devices. New formulations of polyurethane SMP scaffolds are gaining significant interest for use in vascular embolization procedures. These scaffolds have demonstrated rapid time to occlusion, improved healing, and favorable biocompatibility, and they eliminate the need to implant multiple devices to achieve stable occlusion, significantly reducing procedure times and the total cost of treatment. Described here are various methods used to fabricate SMP scaffolds, indications for SMP scaffold embolization, advantages of using these scaffolds in embolization procedures, results seen in animal studies that made use of SMP scaffolds, and future directions for SMP scaffolds that will propel the technology to significant use beyond vessel occlusion.

Dow Corning SE 1700 (reinforced polydimethylsiloxane) porous structures were made by direct ink writing (DIW). The specimens (~50% porosity) were subjected to various compressive strains (15, 30, 45%) and temperatures (room temperature, 35, 50, 70°C) in a nitrogen atmosphere (active purge) for 1 year. Compression set and load retention of the aged specimens were measured periodically during the study. Compression set increased with strain and temperature. After 1 year, specimens aged at room temperature, 35, and 50°C showed ~10% compression set (relative to the applied compressive deflection), while those aged at 70°C showed 20-40%. Due to the increasing compression set, load retention decreased with temperature, ranging from ~90% at room temperature to ~60-80% at 70°C. Long-term compression set and load retention at room temperature were predicted by applying time-temperature superposition (TTS). The predictions show compression set relative to the compressive deflection will be ~10-15% with ~70-90% load retention after 50 years at 15-45% strain, suggesting the material will continue to be mechanically functional. Comparison of the results to previously acquired data for cellular (M97*, M9760, M9763) and RTV (S5370) silicone foams suggests that the SE 1700 DIW porous specimens are on par with, or outperform, the legacy foams.

Silicone elastomers have broad versatility within a variety of potential advanced materials applications, such as soft robotics, biomedical devices, and metamaterials. A series of custom 3D printable silicone inks with tunable stiffness is developed, formulated, and characterized. The silicone inks exhibit excellent rheological behavior for 3D printing, as observed from the printing of porous structures with controlled architectures. Herein, the capability to tune the stiffness of printable silicone materials via careful control over the chemistry, network formation, and crosslink density of the ink formulations in order to overcome the challenging interplay between ink development, post-processing, material properties, and performance is demonstrated.