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Concept: Polymers


Inspired by natural muscle, a key challenge in soft robotics is to develop self-contained electrically driven soft actuators with high strain density. Various characteristics of existing technologies, such as the high voltages required to trigger electroactive polymers ( > 1KV), low strain ( < 10%) of shape memory alloys and the need for external compressors and pressure-regulating components for hydraulic or pneumatic fluidicelastomer actuators, limit their practicality for untethered applications. Here we show a single self-contained soft robust composite material that combines the elastic properties of a polymeric matrix and the extreme volume change accompanying liquid-vapor transition. The material combines a high strain (up to 900%) and correspondingly high stress (up to 1.3 MPa) with low density (0.84 g cm(-3)). Along with its extremely low cost (about 3 cent per gram), simplicity of fabrication and environment-friendliness, these properties could enable new kinds of electrically driven entirely soft robots.The development of self-contained electrically driven soft actuators with high strain density is difficult. Here the authors show a single self-contained soft robust composite material that combines the elastic properties of a polymeric matrix and the extreme volume change accompanying liquid vapour transition.

Concepts: Density, Water, Polymer, Soft matter, Metallurgy, Pseudoelasticity, Polymers, Electroactive polymers


The creation of reversibly-actuating components that alter their shapes in a controllable manner in response to environmental stimuli is a grand challenge in active materials, structures, and robotics. Here we demonstrate a new reversible shape-changing component design concept enabled by 3D printing two stimuli responsive polymers-shape memory polymers and hydrogels-in prescribed 3D architectures. This approach uses the swelling of a hydrogel as the driving force for the shape change, and the temperature-dependent modulus of a shape memory polymer to regulate the time of such shape change. Controlling the temperature and aqueous environment allows switching between two stable configurations - the structures are relatively stiff and can carry load in each - without any mechanical loading and unloading. Specific shape changing scenarios, e.g., based on bending, or twisting in prescribed directions, are enabled via the controlled interplay between the active materials and the 3D printed architectures. The physical phenomena are complex and nonintuitive, and so to help understand the interplay of geometric, material, and environmental stimuli parameters we develop 3D nonlinear finite element models. Finally, we create several 2D and 3D shape changing components that demonstrate the role of key parameters and illustrate the broad application potential of the proposed approach.

Concepts: Engineering, Control, Inkjet printer, Mystique, 3D printing, Polymers, Shapeshifting, Werewolf


Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers - digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications.

Concepts: Temperature, Thermodynamics, Printing, Paper, Shape memory alloy, Polymers, Printmaking, Shape memory polymer


We present a new 4D printing approach that can create high resolution (up to a few microns), multimaterial shape memory polymer (SMP) architectures. The approach is based on high resolution projection microstereolithography (PμSL) and uses a family of photo-curable methacrylate based copolymer networks. We designed the constituents and compositions to exhibit desired thermomechanical behavior (including rubbery modulus, glass transition temperature and failure strain which is more than 300% and larger than any existing printable materials) to enable controlled shape memory behavior. We used a high resolution, high contrast digital micro display to ensure high resolution of photo-curing methacrylate based SMPs that requires higher exposure energy than more common acrylate based polymers. An automated material exchange process enables the manufacture of 3D composite architectures from multiple photo-curable SMPs. In order to understand the behavior of the 3D composite microarchitectures, we carry out high fidelity computational simulations of their complex nonlinear, time-dependent behavior and study important design considerations including local deformation, shape fixity and free recovery rate. Simulations are in good agreement with experiments for a series of single and multimaterial components and can be used to facilitate the design of SMP 3D structures.

Concepts: Polymer, Polymer chemistry, Differential scanning calorimetry, Glass, Glass transition, Shape memory alloy, Polymers, Shape memory polymer


Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations.

Concepts: Psychology, Series, Physics, Structure, Sequence, Universe, Polymers, Finite set


The Mediterranean Sea has been recently proposed as one of the most impacted regions of the world with regards to microplastics, however the polymeric composition of these floating particles is still largely unknown. Here we present the results of a large-scale survey of neustonic micro- and meso-plastics floating in Mediterranean waters, providing the first extensive characterization of their chemical identity as well as detailed information on their abundance and geographical distribution. All particles >700 μm collected in our samples were identified through FT-IR analysis (n = 4050 particles), shedding for the first time light on the polymeric diversity of this emerging pollutant. Sixteen different classes of synthetic materials were identified. Low-density polymers such as polyethylene and polypropylene were the most abundant compounds, followed by polyamides, plastic-based paints, polyvinyl chloride, polystyrene and polyvinyl alcohol. Less frequent polymers included polyethylene terephthalate, polyisoprene, poly(vinyl stearate), ethylene-vinyl acetate, polyepoxide, paraffin wax and polycaprolactone, a biodegradable polyester reported for the first time floating in off-shore waters. Geographical differences in sample composition were also observed, demonstrating sub-basin scale heterogeneity in plastics distribution and likely reflecting a complex interplay between pollution sources, sinks and residence times of different polymers at sea.

Concepts: Polymer, Plastic, Polypropylene, Plastics, Thermoplastic, Polyethylene terephthalate, Polymers, Thermoplastics


Pluronic F127/poly(aspartic acid) mixtures were investigated in dilute solutions by viscometry and dynamic light scattering. The two polymers were chosen due to well known applications in biomedical field, taking into account the final purpose (the use of the complex structure as drug delivery systems). The central item was to identify the possibility of complexation between the poly(carboxylic acid) and a non-ionic polymer and to investigate the conditions of the interpolymer complex formation. The ability of Pluronic F127 to form micelle is well known. Poly(aspartic acid), as a polycarboxylic acid with resemblance with polyacrylic acid, can act as dispersant, antiscalant, superabsorber, being also able to form micelles. Due to its functional groups, COOH and NH(2), poly(aspartic acid) can make physical and/or chemical bonds with other macromolecular compounds. The intrinsic viscosity and the dynamic light scattering data obtained for PLU/PAS mixtures at 25°C have shown that interpolymer complex formation occurs around 1/1wt. ratio between the two polymers.

Concepts: Concentration, Chemistry, Chemical compound, Colloidal chemistry, Light scattering, Dynamic light scattering, Rayleigh scattering, Polymers


In this study, nano sensitively fabricated metallic micro device was combined with conventional micromolding technique in order to assemble polymeric micro needle arrays. We describe the polymer selection and optimization of the fabrication parameters for dissolvable, swellable, and biodegradable polymeric microneedle arrays. Sodium alginate (SA), hydroxypropyl cellulose (H and M grades), cross-linked polyvinyl alcohol with gelatin, chitosan, and polylactic-co-glycolic acid (PLGA) polymers were used to microfabricate solid, out-of-plane, polymeric microneedles from pyramidal male master templates of the following dimensions: 900-μm height, 250-μm needle base width, 500-μm interneedle base spacing. The dimensions of theoretical and measured microarrays were found to be similar. With regard to height, PLGA microneedle fabrication was 10 and 5 times more precise than chitosan and SA microneedle fabrication, respectively. Mechanical failure of SA and PLGA polymeric microneedles was investigated. The fracture forces were approximately 5 times less for SA microneedles than for PLGA microneedles.

Concepts: Polymer, Cell wall, Polysaccharide, Excipients, Polyethylene terephthalate, Microfabrication, Polymers, Polyvinyl butyral


The phase behavior of two types of poly(ethylene oxide)/ poly(propylene oxide) (PEO/PPO) copolymers in aqueous solutions was studied by light scattering, viscometry and infrared spectroscopy. Both the reverse poloxamer (Pluronic 10R5) and the star type poloxamine (Tetronic 90R4) have practically the same PEO/PPO ratio with their hydrophobic blocks (PPO) located in the outer part. The temperature-composition phase diagrams show that both 10R5 and 90R4 tend to form aggregates in water. Up to four different phases can be detected in the case of Tetronic 90R4 for each temperature: unimers, random networks, micellar networks and macrophase separation. Viscometric and infrared measurements complemented the results obtained by light scattering and visual inspection.

Concepts: Spectroscopy, Concentration, Solutions, Triple point, Near infrared spectroscopy, Polymers, Poloxamer, Poloxamer 407


Polymeric micelles were studied as delivery carriers of diazepam, a practically insoluble drug in water, for rectal administration. The diazepam-loaded polymeric micelles were developed by using poloxamer 407 (P407), poloxamer 188, and D-α-tocopheryl poly(ethylene glycol) 1000 succinate (TPGS). Among the used polymers, TPGS resulted in polymeric micelles with good characteristics for encapsulation of diazepam which had the small particle size of 8-12 nm and narrow size distribution (PI 0.053-0.275). Additionally, 7.5% w/v of TPGS could entirely entrap the desired concentration of diazepam (5 mg/mL). To improve the physical stability upon lyophilization, an addition of P407 of 1% w/v prevented aggregation, increased physical stability, and maintained chemical stability of the lyophilized powders of diazepam-loaded polymeric micelles for 3 months storage at 4°C. The rate and amount of diazepam release from TPGS polymeric micelles mainly depended on the concentration of TPGS. The release data were fitted to Higuchi’s model suggesting that the drug release mechanism was controlled by Fickian diffusion. In conclusion, 10% w/v TPGS and 1% w/v P407 were the optimum formulation of lyophilized diazepam-loaded polymeric micelles.

Concepts: Polymer, Particle size distribution, Solution, Freeze drying, Sublimation, Polymers, Poloxamer, Poloxamer 407