Click chemistry stereolithography for soft robots that self-heal.

Although soft robotics promises a new generation of robust, versatile machines capable of complex functions and seamless integration with biology, the fabrication of such soft, three dimensional (3D) hierarchical structures remains a significant challenge. Stereolithography (SLA) is an additive manufacturing technique that can rapidly fabricate the complex device architectures required for the next generation of these systems. Current SLA materials and processes are prohibitively expensive, display little elastic deformation at room temperature, or exhibit Young's moduli exceeding most natural tissues, all of which limit use in soft robotics. Herein, we report a low-cost build window substrate that enables the rapid fabrication of high resolution (∼50 µm) silicone (polydimethylsiloxane) based elastomeric devices using an open source SLA printer. Our thiol-ene click chemistry permits photopolymerization using low energy (He < 20 mJ cm-2) optical wavelengths (405 nm < λ < 1 mm) available on many low-cost SLA machines. This chemistry is easily tuned to achieve storage moduli, 6 < E < 283 kPa at engineering strains, γ = 0.02; similarly, a large range of ultimate strains, 0.5 < γult < 4 is achievable through appropriate selection of the two primary chemical constituents (mercaptosiloxane, M.S., and vinylsiloxane, V.S.). Using this chemo-mechanical system, we directly fabricated compliant machines, including an antagonistic pair of fluidic elastomer actuators (a primary component in most soft robots). During printing, we retained unreacted pockets of M.S. and V.S. that permit autonomic self-healing, via sunlight, upon puncture of the elastomeric membranes of the soft actuators.

CO2 sorption kinetics of scaled-up polyethylenimine-functionalized mesoporous silica sorbent.

Two CO2 solid sorbents based on polyethylenimine, PEI (M(n) ∼ 423 and 10K), impregnated into mesoporous silica (MPS) foam prepared in kilogram quantities via a scale-up process were synthesized and systematically characterized by a range of analytical and surface techniques. The mesoporous silica sorbent impregnated with lower molecular weight PEI, PEI-423/MPS, showed higher capacity toward CO2 sorption than the sorbent functionalized with the higher molecular weight PEI (PEI-10K/MPS). On the other hand, PEI-10K/MPS exhibited higher thermal stability than PEI-423/MPS. The kinetics of CO2 adsorption on both PEI/MPS fitted well with a double-exponential model. According to this model CO2 adsorption can be divided into two steps: the first is fast and is attributed to CO2 adsorption on the sorbent surface; the second is slower and can be related to the diffusion of CO2 within and between the mesoporous particles. In contrast, the desorption process obeyed first-order kinetics with activation energies of 64.3 and 140.7 kJ mol(-1) for PEI-423/MPS and PEI-10K/MPS, respectively. These studies suggest that the selection of amine is critical as it affects not only sorbent capacity and stability but also the energy penalty associated with sorbent regeneration.

Quasielastic neutron scattering of poly(methyl phenyl siloxane) in the bulk and under severe confinement.

Quasielastic neutron scattering was utilized to investigate the influence of confinement on polymer dynamics. Poly(methyl phenyl siloxane) chains were studied in the bulk as well as severely confined within the approximately 1-2 nm interlayer spacing of intercalated polymer/layered organosilicate nanohybrids. The temperature dependence of the energy resolved elastic scattering measurements for the homopolymer and the nanocomposites exhibit two distinct relaxation steps: one due to the methyl group rotation and one that corresponds to the phenyl ring flip and the segmental motion. Quasielastic incoherent measurements show that the very local process of methyl rotation is insensitive to the polymer glass transition temperature and exhibits a wave-vector independent relaxation time and a low activation energy, whereas it is not affected at all by the confinement. At temperatures just above the calorimetric glass transition temperature, the observed motion is the phenyl ring motion, whereas the segmental motion is clearly identified for temperatures about 60 K higher than the glass transition temperature. For the nanohybrid, the segmental motion is found to be strongly coupled to the motion of the surfactant chains for temperatures above the calorimetric glass transition temperature of the bulk polymer. However, the mean square displacement data show that the segmental motion in confinement is faster than that of the bulk polymer even after the contribution of the surfactant chains is taken into consideration.

Magnetic resonance in nanoparticles: between ferro- and paramagnetism.

Magnetic nanoparticles of γ-Fe(2)O(3) coated with organic molecules and suspended in liquid and solid matrices, as well as non-diluted magnetic fluid, have been studied by electron magnetic resonance (EMR) at 77-380 K. Slightly asymmetric spectra observed at room temperature become much broader and symmetric, and shift to lower fields upon cooling. An additional narrow spectral component (with a line-width of 30 G) is found in diluted samples; its magnitude obeys the Arrhenius law with an activation temperature of about 850 K. The longitudinal spin-relaxation time, T(1)≈10 ns, is determined by a specially developed modulation method. The angular dependence of the EMR signal position in field-freezing samples points to substantial alignment, suggesting the formation of dipolar-coupled aggregates. The shift and broadening of the spectrum upon cooling are assigned to the effect of the surface-related anisotropy. To describe the overall spectral shape, the 'quantization' model is used which includes summation of resonance transitions over the whole energy spectrum of a nanoparticle considered as a giant exchange cluster. This approach, supplemented with some phenomenological assumptions, provides satisfactory agreement with the experimental data.

NMR and spin relaxation in systems with magnetic nanoparticles.

The ¹H NMR spectra and spin dynamics of the host systems have been studied in liquid and solid suspensions of γ-Fe2O3 nanoparticles. Significant broadening of ¹H NMR spectra and growing relaxation rates were observed with increased concentration of nanoparticles in the liquid systems, with the relation T1/T2 depending on the particular host. Solid systems demonstrate inhomogeneous broadening of the spectra and practically no dependence of T1 upon the nanoparticle concentration. We explain the experimental results taking into account the predomination of self-diffusion as a source of the relaxation in liquid suspensions, and estimate effective parameters of relaxation in the systems under study.

Surface-functionalized nanoparticles with liquid-like behavior: the role of the constituent components.

Ionically modified silica nanoparticles with large counter anions (sulfonate, isostearate) at two silica volume fractions (13 and 27%) form a viscous fluid and a glass but not crystalline solids. Dielectric spectroscopy, Brillouin scattering and shear rheometry were employed to investigate these new nanoparticle-based fluids. The glass transition temperature and hence the local dynamics are governed by the large counter anions, whereas the flow properties can be controlled by the spatial correlation between the nanoparticles, e.g. by tuning the volume fraction of hard cores and local interactions between segments in the soft corona. Liquid-like ordering of the cores was revealed by X-ray scattering and found to influence significantly the macroscopic flow properties of these salts.

Structure and dynamics of polymer-grafted clay suspensions.

The structure and dynamics of polymer-grafted two-dimensional silicate layers in solution were investigated. The geometry of the individual silicate layers was examined by looking at both polarized and depolarized light scattering from dilute solutions, while higher-concentration systems were used to study the interaction and dynamics of polymer-grafted silicate layers in suspension. The form factor for an oblate ellipsoid was used to fit the polarized intensity profile, and values of a approximately 80 nm and b approximately 380 nm for the semi-axes were obtained. The 80 nm value compares reasonably with the dimensions of the polymer brushes grafted on the surface of the silicate layers. The modulus of the grafted silicate in solution, as determined by Brillouin scattering, is of the order of 10 GPa. The cooperative diffusion mechanism, typical of interacting polymer chains, is suppressed due to the high polymer osmotic pressure. The osmotic pressure is also responsible for the weak interpenetration of the densely grafted polymer chains on the surface of the silicate layers. The scattering data indicates that the polymer-grafted nanoparticles move via collective diffusion and experience significant decrease in mobility above their overlap concentration.

Matrix-Mediated Synthesis of Nanocrystalline ggr-Fe2O3: A New Optically Transparent Magnetic Material.

A new magnetic material with appreciable optical transmission in the visible region at room temperature has been isolated as a gamma-Fe(2)O(3)/polymer nanocomposite. The synthesis is carried out in an ion-exchange resin at 60 degrees C. Magnetization and susceptibility data demonstrate loading-dependent saturation moments as high as 46 electromagnetic units per gram and superparamagnetism for lower loadings where particle sizes are less than 100 angstroms. Optical absorption studies show that the small-particle form of gamma-Fe(2)O(3) is considerably more transparent to visible light than the single-crystal form. The difference in absorption ranges from nearly an order of magnitude in the "red" spectral region to a factor of 3 at 5400 angstroms. The magnetization of the nanocomposite is greater by more than an order of magnitude than those of the strongest room-temperature transparent magnets, FeBO(3) and FeF(3).

Optical fiber measurements of particle velocity using laser-induced phosphorescence.

An optical fiber anemometer that uses laser-induced phosphorescence to measure particle time of flight in dense gas-solid suspensions is described. The anemometer is tested using a spinning disk coated with a phosphor having a persistent afterglow. The diagnostic technique is illustrated by measuring the velocity of free-falling particles coated with the same phosphor. Monte Carlo simulations are employed to determine the optical characteristics of the probe, including its measurement volume.