Polydimethylsiloxane (PDMS) has emerged as a promising candidate for the dielectric layer in implantable sensors due to its exceptional biocompatibility, stability, and flexibility. This study introduces an innovative approach to produce graphene-reinforced PDMS (Gr-PDMS), where graphite powders are exfoliated into mono- and few-layer graphene sheets within the polymer solution, concurrently forming cross-linkages with PDMS. This method yields a uniformly distributed graphene within the polymer matrix with improved interfaces between graphene and PDMS, significantly reducing the percolation threshold of graphene dispersed in PDMS from 10% to 5%. As-synthesized Gr-PDMS exhibits improved mechanical and electrical properties, tested for potential use in capacitive pressure sensors. The results demonstrate an impressive pressure sensitivity up to 0.0273 kpa-1, 45 times higher than that of pristine PDMS and 2.5 times higher than the reported literature value. The Gr-PDMS showcases excellent pressure sensing ability and stability, fulfilling the requirements for implantable intracranial pressure (ICP) sensors.
In phase-selective laser-induced breakdown spectroscopy (PS-LIBS), gas-borne nanoparticles are irradiated with laser pulses (â¼2.4 GW/cm2) resulting in breakdown of the nanoparticle phase but not the surrounding gas phase. In this work, the effect of excitation laser-pulse duration and energy on the intensity and duration of TiO2-nanoparticle PS-LIBS emission signal is investigated. Laser pulses from a frequency-doubled neodymium-doped yttrium aluminum garnet (Nd:YAG) laser (532 nm) are stretched from 8 ns (full width at half maximum, FWHM) up to â¼30 ns at fixed pulse energy using combinations of two optical cavities. The intensity of the titanium atomic emissions at around 500 nm wavelength increases by â¼60%, with the stretched pulse and emissions at around 482 nm, attributed to TiO, enhanced over 10 times. While the atomic emissions rise with the stretched laser pulse and decay around 20 ns after the end of the laser pulse, the TiO emissions reach their peak intensity at about 20 ns later and last longer. At low laser energy (i.e., 1 mJ/pulse, or 80 MW/cm2), the TiO emissions dominate, but their increase with laser energy is lower compared to the atomic emissions. The origin of the 482 nm emission is explored by examining several different aerosol setups, including Ti-O, Ti-N, and Ti-O-N from a spark particle generator and Ti-O-N-C-H aerosol from flame synthesis. The 482 nm emissions are attributed to electronically excited TiO, likely resulting from the reaction of excited titanium atoms with surrounding oxidizing (carbonaceous and/or radical) species. The effects of pulse length are attributed to the shift of absorption from the initial interaction with the particle to the prolonged interaction with the plasma through inverse bremsstrahlung.
Effective methods are needed to fabricate the next generation of high-performance graphene-reinforced polymer matrix composites (G-PMCs). In this work, a versatile and fundamental process is demonstrated to produce high-quality graphene-polymethylmethacrylate (G-PMMA) composites via in situ shear exfoliation of well-crystallized graphite particles loaded in highly-viscous liquid PMMA/acetone solutions into graphene nanoflakes using a concentric-cylinder shearing device. Unlike other methods where graphene is added externally to the polymer and mixed, our technique is a single step process where as-exfoliated graphene can bond directly with the polymer with no contamination/handling. The setup also allows for the investigation of the rheology of exfoliation and dispersion, providing process understanding in the attainment of the subsequently heat injection-molded and solidified G-PMC, essential for future manufacturing scalability, optimization, and repeatability. High PMMA/acetone concentration correlates to high mixture viscosity, which at large strain rates results in very-high shear stresses, producing a large number of mechanically-exfoliated flakes, as confirmed by liquid-phase UV-visible spectral analysis. Raman spectroscopy and other imaging evince that single- and bi-layer graphene are readily achieved. Nevertheless, a limit is reached at high mixtures viscosities where the process becomes unstable as non-Newtonian fluid behavior (e.g. viscoelastic) dominates the system. Characterization of microstructure, morphology, and properties of this new class of nanostructured composites reveals interesting trends. Observations by transmission electron microscopy, scanning electron microscopy, and helium ion microscopy of the manufactured G-PMCs show uniform distributions of unadulterated, well-bonded, discontinuous, graphene nanoflakes in a PMMA matrix, which enhances stiffness and strength via a load-transfer mechanism. Elastic modulus of 5.193 GPa and hardness of 0.265 GPa are achieved through processing at 0.7 g ml-1 of acetone/PMMA for 1% wt. starting graphite loading when injected into a sample mold at 200 °C. Mechanical properties exhibit 31% and 28.6% enhancement in elastic modulus and hardness, respectively, as measured by nano-indentation.
The relative stability and melting of cubic boron nitride (c-BN) nanoparticles of varying shapes and sizes are studied using classical molecular dynamics (MD) simulation. Focusing on the melting of octahedral c-BN nanoparticles, which consist solely of the most stable {111} facets, decomposition is observed to occur during melting, along with the formation of phase segregated boron clusters inside the c-BN nanoparticles, concurrent with vaporization of surface nitrogen atoms. To assess this MD prediction, a laser-heating experiment of c-BN powders is conducted, manifesting boron clusters for the post-treated powders. A general analysis of the geometrical and surface dependence of the nanoparticle ground-state energy using a Stillinger-Weber potential determines the relative stability of cube-shaped, octahedral, cuboctahedral, and truncated-octahedral c-BN nanoparticles. This stability is further examined using transient MD simulations of the melting behavior of the differently shaped nanoparticles, providing insights and revealing the key roles played by corner and edge initiated disorder as well as surface reconstruction from {100} to the more stable {111} facets in the melting process. Finally, the size dependence of the melting point of octahedral c-BN nanoparticles is investigated, showing the well-known qualitative trend of depression of melting temperature with decreasing size, albeit with different quantitative behavior from that predicted by existing analytical models.
Heterostructures of tungsten-oxide nanowires decorated with zinc/tin-oxide nanostructures are synthesized via a combined flame and solution synthesis approach. Vertically well-aligned tungsten-oxide nanowires are grown on a tungsten substrate by a flame synthesis method. Here, tetragonal WO(2.9) nanowires (diameters of 20-50 nm, lengths >10 µm, and coverage density of 10(9)-10(10) cm(-2)) are produced by the vapor-solid mechanism at 1720 K. Various kinds of Zn/Sn-oxide nanostructures are grown or deposited on the WO(2.9) nanowires by adjusting the Sn(2+) : Zn(2+) molar ratio in an aqueous ethylenediamine solution at 65 °C. With WO(2.9) nanowires serving as the base structures, sequential growth or deposition on them of hexagonal ZnO nanoplates, Zn(2)SnO(4) nanocubes, and SnO(2) nanoparticles are attained for Sn(2+) : Zn(2+) ratios of 0 : 1, 1 : 10, and 10 : 1, respectively, along with different saturation conditions. High-resolution transmission electron microscopy of the interfaces at the nanoheterojunctions shows abrupt interfaces for ZnO/WO(2.9) and Zn(2)SnO(4)/WO(2.9), despite lattice mismatches of >20%.
The absorption-ablation-excitation mechanism in laser-cluster interactions is investigated by measuring Rayleigh scattering of aerosol clusters along with atomic emission from phase-selective laser-induced breakdown spectroscopy. For 532 nm excitation, as the laser intensity increases beyond 0.16 GW/cm^{2}, the scattering cross section of TiO_{2} clusters begins to decrease, concurrent with the onset of atomic emission of Ti, indicating a scattering-to-ablation transition and the formation of nanoplasmas. With 1064 nm laser excitation, the atomic emissions are more than one order of magnitude weaker than that at 532 nm, indicating that the thermal effect is not the main mechanism. To better clarify the process, time-resolved measurements of scattering signals are examined for different excitation laser intensities. For increasing laser intensity, the cross section of clusters decreases during a single pulse, evincing the shorter ablation delay time and larger ratios of ablation clusters. Assessment of the electron energy distribution during the ablation process is conducted by nondimensionalizing the Fokker-Planck equation, with analogous Strouhal Sl_{E}, Peclet Pe_{E}, and Damköhler Da_{E} numbers defined to characterize the laser-induced aerothermochemical environment. For conditions where Sl_{E}â«1, Pe_{E}â«1, and Da_{E}âª1, the electrons are excited to the conduction band by two-photon absorption, then relax to the bottom of the conduction band by electron energy loss to the lattice, and finally serve as the energy transfer media between laser field and lattice. The relationship between delay time and excitation intensity is well correlated by this simplified model with quasisteady assumption.
A nanostructured thermite composite comprising an array of tungsten-oxide (WO2.9) nanowires (diameters of 20-50 nm and lengths of >10 µm) coated with single-crystal aluminum (thickness of ~16 nm) has been fabricated. The method involves combined flame synthesis of tungsten-oxide nanowires and ionic-liquid electrodeposition of aluminum. The geometry not only presents an avenue to tailor heat-release characteristics due to anisotropic arrangement of fuel and oxidizer but also eliminates or minimizes the presence of an interfacial Al2O3 passivation layer. Upon ignition, the energetic nanocomposite exhibits strong exothermicity, thereby being useful for fundamental study of aluminothermic reactions as well as enhancing combustion characteristics.
Aluminum Oxide/chemistry , Nanowires/chemistry , Oxides/chemistry , Tungsten/chemistry , Microscopy, Electron, Scanning , Nanotechnology , Nanotubes/chemistry , Thermodynamics
In contrast to van der Waals (vdW) forces, Coulombic dipolar forces may play a significant role in the coagulation of nanoparticles (NPs) but has received little or no attention. In this work, the effect of dipole-dipole interaction on the enhancement of the coagulation of two spherically shaped charge-neutral TiO(2) NPs, in the free molecular regime, is studied using classical molecular dynamics (MD) simulation. The enhancement factor is evaluated by determining the critical capture radius of two approaching NPs for different cases of initial dipole direction with respect to path (parallel∕perpendicular) and orientation with respect to each other (co-orientated∕counterorientated). As particle diameter decreases, the enhancement of coagulation is augmented as the ratio of dipole-dipole force to vdW force becomes larger. For 2-nm TiO(2) NPs at 273 K, the MD simulation predicts an average enhancement factor of about 8.59, which is much greater than the value of 3.78 when only the vdW force is considered. Nevertheless, as temperature increases, the enhancement factor due to dipole-dipole interaction drops quickly because the time-averaged dipole moment becomes small due to increased thermal fluctuations (in both magnitude and direction) of the instantaneous dipole moment.
