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This presentation covers the use of smart materials in Naval Research Laboratory (NRL) research for sensors, actuators, and modeling and control. Emphasis is on optical fiber Bragg gratings, piezoelectric actuators, shape memory alloy actuators, and polymer matrix and interfaces.
Microscale, pick-and-place assembly is a non-lithographic assembly method poised to impact diverse fields including flexible electronics, microfluidics and robotics. However, a major technological challenge is the need to deterministically control adhesion between parts. Here, switchable adhesion involving 3D-printed, self-complementary surfaces is demonstrated. Mechanical properties of metasurfaces pressed against flat, rigid substrates are modeled using finite element methods. A series of flat slabs and metastructured slabs with 2D sinusoidal surfaces are printed using two-photon polymerization (2PP) of a shape-memory resin. The surface frequency of featured slabs was varied between $3.\bar3$ mm −1 and $26.\bar6$ mm −1 with similar amplitudes. Adhesion between printed metasurfaces and glass and between printed, self-complementary metasurfaces is studied above and below the cured resin’s glass transition temperature (∼45 °C). Simple heating of adhering surfaces to above 60 °C lowers adhesion, and compression of surfaces while above the glass transition temperature followed by cooling to room temperature elevates adhesion. The nominal adhesive strength between printed, self-complementary surfaces, as determined by the maximum observable pull-off stress, exceeds 3 MPa. Further tailoring complementary surfaces for adhesion control may facilitate microscale disassembly for recovery of components or precious metals.
Concrete is the most used man-made material today consisting of a mixture of aggregates (sand, gravel, crashed rock) and paste. The paste component, made up of cement and water, cracks with time. Despite this shortcoming, research towards next-generation cement and concrete has only taken a boost in the past 10-15 years. In particular, self-healing cementitious materials is a research area that has attracted a great deal of attention. A number of reported novel formulations have demonstrated an increase in mechanical and chemical stability with respect to conventional Portland cement, through the addition of inorganic, organic, and even biological additives. This review reports on the latest advances in cement research related to the synthesis of self-healing cements applied in concrete structures. These include geopolymers, engineered cementitious materials (ECC), bacterial cement composites, microencapsulated self-healing materials, shape memory alloys (SMA), and polymer-cement composites. This work describes the performance of each cementitious material and the mechanism responsible for self-healing, including a section on the latest computational modeling studies towards this end. A detailed understanding of these various self-healing cement technologies, including their strengths and weaknesses, is critical at the time of determining the type of structures that these materials could be used for.
A single sheet of nickel-titanium (NiTi) shape memory alloy (SMA) was introduced within an IM7/8552 polymer matrix composite (PMC) panel in conjunction with multiple thin film adhesives to promote the interfacial bond strength between the SMA and PMC. End notched flexure (ENF) testing was performed in accordance to ASTM D7905 method for evaluation of mode II interlaminar fracture toughness (GIIC) of unidirectional fiber-reinforced polymer matrix composites. Acoustic emissions (AE) were monitored during testing with two acoustic sensors attached to the specimens. The composite panels were subjected to C-scan before testing, and examined using optical and scanning electron microscopy techniques after part failure. GIIC values for the control composite samples were found to be higher than those of samples with embedded SMA sheets. The presence of adhesives bonded to SMA sheets further diminished the GIIC values. AE values revealed poor bonding of the panels, with little to no signals during testing.
Shape Memory Alloy (SMA) was placed within Polymer Matrix Composite (PMC) panels alongside film adhesives to examine bonding. Double cantilever beam (DCB) testing was performed using ASTM D5528. C-scanning was performed before testing, modal acoustic emissions (MAE) were monitored during testing, and microscopy performed post-test. Data was analyzed using modified beam theory (MBT), compliance calibration (CC) and modified compliance calibration (MCC) methods. Fracture toughness for control specimens was higher than previously reported due to fiber-bridging. Specimens with SMAs and adhesives stabilized crack propagation. Results revealed SMA-bridging; a phenomenon mimicking fiber-bridging which increased the load and fracture toughness of SMA specimens.
Approaches to optimize the adhesive joint strength between shape memory alloy ribbons and carbon fiber-reinforced epoxy composites were investigated for potential use as either an actuating structure or a dampening composite for structural applications. The interfacial bond strength between nickel-titanium (NiTi) and a polymer matrix composite (PMC) was measured by double lap shear testing as a function of NiTi surface treatment and adhesive material. The effect of NiTi surface treatment on damping was investigated using dynamic mechanical analysis. Lap shear data show that treating the surfaces of NiTi ribbons by light sandblasting and primer application increased the interfacial bond strength by 20 percent over the baseline composite structure. Lap shear data also reveal that out of three different film adhesives investigated, samples bonded with AF 191U and Hysol® 9696U display the highest adhesive joint strengths. Optical microscopy reveals that most samples failed by either cohesive failure within the adhesive or by adhesive failure at either the adhesive/PMC or NiTi/adhesive interface. Adhering NiTi to the PMC did not appear to negatively impact damping performance; however, a more thorough examination into NiTi's role on vibration damping should be investigated.
Shape-memory resists capable of high-resolution curing into arbitrarily designed structures are increasingly demanded for soft robotics, optical sensors, microscale manufacturing, and biomedicine. Amorphous, shape-memory thiol-vinyl networks were printed using two-photon polymerization (2PP) curing of a simple resin formulated with commercially available reagents. The ability to print high-resolution feature sizes down to 200 nm is attributed to the use of radicalmediated, thiol-vinyl step-growth polymerization that quickly crosslinks the resin, limiting diffusive transport. The thermomechanical behavior of the 2PP-cured material analyzed in compression, tension and three-point bending is similar to the behavior of the UV-polymerized samples. To demonstrate the ability to design, field, and test 4D responsive microstructures, an array of nine springs with coil diameters of 330 μm was printed. Following compressive shapefixing, printed arrays can release 11 μJ of stored elastic strain energy when reheated. Further, a new concept of dichroic-memory of a metamaterial device is demonstrated by printing a twisted woodpile structure with circular dichroism as characterized by Mueller Matrix ellipsometry. Furthermore, our results demonstrate how combining high-resolution 2PP curing with stimuli-responsive molecular architectures can further the engineering of responsive microstructures and metamaterials.
The Office of Education at NASA Headquarters provides overall policy and direction for the NASA Faculty Fellowship Program (NFFP). The American Society for Engineering Education (ASEE) and the Universities Space Research Association (USRA) have joined in partnership to recruit participants, accept applications from a broad range of participants, and provide overall evaluation of the NFFP. The NASA Centers, through their University Affairs Officers, develop and operate the experiential part of the program. In concert with co-directing universities and the Centers, Fellows are selected and provided the actual research experiences. This report summarizes the 2003 session conducted at the Glenn Research Center (GRC).Research topics covered a variety of areas including, but not limited to, biological sensors, modeling of biological fluid systems, electronic circuits, ceramics and coatings, unsteady probablistic analysis and aerodynamics, gas turbines, environmental monitoring systems for water quality, air quality, gaseous and particulate emissions, bearings for flywheel energy storage, shape memory alloys,photonic interrogation and nanoprocesses,carbon nanotubes, polymer synthesis for fuel cells, aviation communications, algorithm development and RESPlan Database.
A single sheet of nickel-titanium (NiTi) shape memory alloy (SMA) was introduced within an IM7/8552 polymer matrix composite (PMC) panel in conjunction with multiple thin film adhesives to promote the interfacial bond strength between the SMA and PMC. End notched flexure (ENF) testing was performed in accordance to ASTM D7905 method for evaluation of mode II interlaminar fracture toughness (GIIC) of unidirectional fiber-reinforced polymer matrix composites. Acoustic emissions (AE) were monitored during testing with two acoustic sensors attached to the specimens. The composite panels examined using scanning electron microscopy techniques after part failure. GIIC values for the control composite samples were found to be higher than those of samples with embedded SMA sheets. The presence of adhesives bonded to SMA sheets further diminished the GIIC values. AE values revealed poor bonding of the panels, with little to no signals during testing.
Developing circular multifunctional vitrimers and carbon fiber–reinforced polymers (CFRPs) that are simultaneously recyclable, mechanically robust, and intrinsically flame retardant remains a major challenge. Here, in this study, we report multifunctional vitrimers and their carbon fiber–reinforced vitrimer (CFRV) composites, where the vitrimer design integrates closed-loop recyclability, enhanced interfacial adhesion, and intrinsic flame retardancy within a single materials platform. The vitrimer matrix is synthesized from post-consumer polyethylene terephthalate (PET) waste and a vanillin-derived phosphorus-containing crosslinker, forming an imine-based network. The resulting vitrimer resin exhibits high tensile strength, thermal healability, repeated reprocessability, programmable shape memory, and rapid chemical depolymerization under mild conditions. Amine-functionalized carbon fibers significantly improve fiber–matrix interfacial bonding, yielding CFRVs with tensile strengths up to 789 MPa and complete recovery of structurally intact fibers after chemical recycling. The phosphorus-rich aromatic network further imparts intrinsic flame retardancy, enabling self-extinguishing behavior without external additives. This work advances a materials design paradigm for next-generation multifunctional, sustainable vitrimers and CFRVs, while simultaneously addressing the recycling challenges associated with both plastic and CFRP waste.
A single sheet of NiTi shape memory alloy (SMA) was introduced within a unidirectional HexPly® 8552/IM7 (Hexcel®) polymer matrix composite (PMC) panel in conjunction with multiple thin-film adhesives to promote the interfacial bond strength between the SMA and PMC. A double cantilever beam (DCB) test was performed in accordance with the ASTM D5528 method for evaluation of Mode I interlaminar fracture toughness of unidirectional fiber-reinforced PMCs. The modal acoustic emissions (MAEs) were monitored during testing with two acoustic sensors attached to the specimens. The composite panels were subjected to a C-scan before testing and examined using optical and scanning electron microscopy (SEM) techniques after part failure. The data were used in conjunction with modified beam theory (MBT), the compliance calibration (CC) method, and the modified compliance calibration (MCC) method. The Mode I interlaminar toughness (G(sub IC)) values for control specimens were higher than previously reported and are attributed to extensive fiber bridging during testing. The presence of adhesives with SMA inserts stabilized crack propagation during DCB testing. The results reveal a new phenomenon of SMA bridging, whereby crack propagation would switch from one side of the SMA insert to the other, thus increasing the load and G(sub IC) values of specimens containing SMA.
We report a facile approach to control the shape memory effects and thermomechanical characteristics of a lignin-based multiphase polymer. Solvent fractionation of a syringylpropane-rich technical organosolv lignin resulted in selective lignin structures having excellent thermal stability coupled with high stiffness and melt-flow resistance. The fractionated lignins were reacted with rubber in melt-phase to form partially networked elastomer enabling selective programmability of the material shape either at 70 °C, a temperature that is high enough for rubbery matrix materials, or at an extremely high temperature, 150 °C. Utilizing appropriate functionalities in fractionated lignins, tunable shape fixity with high strain and stress recovery, particularly high-stress tolerance were maintained. Detailed studies of lignin structures and chemistries were correlated to molecular rigidity, morphology, and stress relaxation, as well as shape memory effects of the materials. The fractionation of lignin enabled enrichment of specific lignin properties for efficient shape memory effects that broaden the materials’ application window. Electron microscopy, melt-rheology, dynamic mechanical analysis and ultra-small angle neutron scattering were conducted to establish morphology of acrylonitrile butadiene rubber (NBR)-lignin elastomers from solvent fractionated lignins.
Polyurethanes are among the top six polymers produced in the world and are widely used in the automotive, furniture, construction and appliance industry for their light weight, impact resistance, and insulating properties. However, the use of hazardous diisocyanates used in polyurethane formulations has led many to search for more sustainable alternatives. The lignin component of biomass has been targeted to replace the often toxic and petroleum-derived precursors to polymer synthesis in support of the biorefinery concept where natural materials are used as the feedstock for commodity plastics. The use of lignin is often hampered due to its low reactivity, heterogeneity and the necessity of employing extensive purification and/or functionalization measures to ensure materials are of comparable quality. In this report, a unique method is presented for the synthesis and processing of a non-toxic, non-isocyanate polyurethane foam utilizing unmodified Kraft lignin and a biobased curing agent. Here, raw Kraft lignin is functionalized with green organic carbonates and a non-toxic approach is taken to solubilize the precursors with a curing agent from renewable fatty acids enabling rapid gel-times. For the first time, a NIPU foam from lignin is synthesized while the structure–property relationship of different reaction mixtures is studied demonstrating shape memory capacity and 100% biobased carbon content.
Shape-memory poly(isocyanurate-urethane) (PIR-PUR) aerogels are low-density monolithic nanoporous solids that remember and return to their permanent shape through a heating actuation step. Herein, through structural design at the macro scale, the shape-memory response is augmented with an auxetic effect manifested by a negative Poisson’s ratio of approximately -0.8 at 15% compressive strain. Thus, auxetic shape-memory PIR-PUR monoliths experience volume contraction upon compression at a temperature above the glass transition temperature of the base polymer (Tg ~ 30 °C), and they can be stowed indefinitely in that temporary shape by cooling below Tg. By heating back above Tg, the compressed/shrunk form expands back to their original shape/size. This technology is relevant to a broad range of industries spanning the commercial, aeronautical, and aerospace sectors. The materials are referred to as meta-aerogels and their potential applications include minimally invasive medical devices, soft robotics, and in situations where volume is at a premium, as for example for storage of deployable space structures and planetary habitats during transport to the point of service.
Vitrimer is an innovative class of polymeric materials which demonstrates traditional thermoset-like mechanical and chemical resilience while still being able to flow on demand like a traditional thermoplastic through covalently adaptive dynamic linkages. Herein, high-performance cellulose fiber reinforced vitrimer composites are developed using an epoxy-based vitrimer and natural cellulose paper. The reinforced vitrimer composite was fabricated by impregnating the porous structure of cellulose paper with two curable monomers, followed by in-situ polymerization of the monomers inside the fibrous scaffold. The introduction of hydroxyl group present on the cellulosic framework assisted in a faster topological rearrangement of the crosslinked matrix through transesterification exchange reaction, thus imparting various sought-after properties like shape recovery and recyclability via simple thermal reprocessing. Moreover, the reinforced vitrimer composite exhibits superior tensile properties as high as 90 MPa with 15-25 volume% vitrimer loading due to the interfacial adhesion via ester exchange reaction between the epoxy matrix and functionalities on the cellulosic fibers. Noteworthily, the key ingredients of the resulting composite (i.e., epoxy-based vitrimer and cellulose fibers) can be comfortably recycled without using aggressive chemical treatment, enabling composite to be easily recycled or disposed of at the end of service life and assist in reducing the subsequent manufacturing cost. This study would shed light on the development of a recyclable polymer composite with exceptional mechanical properties while simultaneously demonstrating self-healing and shape memory capabilities.
Shape memory alloy hybrid composites with adaptive-stiffening or morphing functions are simulated using finite element analysis. The composite structure is a laminated fiber-polymer composite beam with embedded SMA ribbons at various positions with respect to the neutral axis of the beam. Adaptive stiffening or morphing is activated via selective resistance heating of the SMA ribbons or uniform thermal loads on the beam. The thermomechanical behavior of these composites was simulated in ABAQUS using user-defined SMA elements. The examples demonstrate the usefulness of the methods for the design and simulation of SMA hybrid composites. Keywords: shape memory alloys, Nitinol, ABAQUS, finite element analysis, post-buckling control, shape control, deflection control, adaptive stiffening, morphing, constitutive modeling, user element
The next generation of space systems will require large apertures in order to image faint targets or cover large areas of Earth. These large apertures must be able to fit inside a launch vehicle fairing, be light enough for launch into orbit, and deploy on orbit with repeatability and reliability. The current state-of-the-art in flight optics is represented by the 4 meter LAMP telescope, with an areal density of 10 km sq m. Development of a Beryllium mirror demonstration article for NGST (Next Generation Space Telescope) at the University of Arizona indicate areal densities of 0.5 kg sq m with flight hardware in the 12 meter range. With progressive improvements in existing deployment, packaging, and structural technologies, the size of optics and reflectors will continue to increase, while mass is reduced. However, without a breakthrough in materials, packaging and/or deployment technologies, the goal for Gossamer structures of 0.1 kg sq m is unachievable for the near and mid-term NASA missions. Membrane technology provides the best hope of achieving such low areal densities. In combination with advances in membrane materials and structures, development of revolutionary techniques for deployment systems can provide significant improvements in large aperture technology. In this paper, the results of a six-month Phase I research effort to demonstrate the application of thin film NiTi to aerospace-qualified membrane and mesh materials are presented. Deposition of shape memory thin film was achieved Astromesh (trademark) metal mesh and CP-1, and optical-quality polymer membrane. Not only was full-coating deposition demonstrated, but also small segment deposition which holds potential for local surface control. Deployment of these materials was also demonstrated, setting the stage for the development of a larger test article.
Spacecraft in low Earth orbit (LEO) are subjected to harsh environmental conditions, including radiation (cosmic rays, ultraviolet, x-ray, and charged particle radiation), micrometeoroids and orbital debris, temperature extremes, thermal cycling, and atomic oxygen (AO). These environmental exposures can result in erosion, embrittlement and optical property degradation, threatening spacecraft performance and durability. To increase our understanding of effects such as AO erosion and radiation induced embrittlement of spacecraft materials, NASA Glenn has developed a series of experiments flown as part of the Materials International Space Station Experiment (MISSE) missions on the exterior of the International Space Station (ISS). These experiments have provided critical LEO space environment durability data such as AO erosion data for many materials and mechanical properties changes after long term space exposure. In continuing these studies, a new experiment called the Polymers and Composites Experiment has been selected for flight on the MISSE-Flight Facility (MISSE-FF). The Polymers and Composites Experiment will be flown as part of the MISSE-9 mission, the inaugural mission of MISSE-FF manifested on SpaceX-14. This experiment includes 138 samples being flown in ram, wake or zenith orientations for space environmental durability assessment. The primary objective is to determine the LEO AO erosion yield, Ey (the volume loss per incident oxygen atom (cm3/atom)), of polymers, composites, and coated samples, as a function of solar irradiation and AO fluence. In addition, epoxy samples with varying levels of ZnO powder are included to study the effect of filler quantity on AO erosion. An AO Scattering Chamber is included to help improve the understanding of AO scattering mechanisms for improved AO undercutting modeling. Indium tin oxide (ITO) coated samples are included to validate the durability of ITO conductive coatings in LEO. Tensile samples of Teflon fluorinated ethylene propylene (FEP) of varying thicknesses and back-surface coatings will be flown in wake and zenith orientations to study radiation embrittlement versus thickness, and the effect of heating on FEP embrittlement. Finally, shape memory composite and cosmic ray shielding samples will be flown for LEO durability assessment. This paper presents an overview of the MISSE-9 Polymers and Composites Experiment.