Patricia A. Heiden

In Situ Electrochemical Lithiation/Delithiation Observation of Individual Amorphous Si Nanorods

In situ electrochemical lithiation and delithiation processes inside a nanobattery consisting of an individual amorphous Si nanorod and ionic liquid were explored. Direct formation of the crystalline Li(22)Si(5) phase due to the intercalation of Li ions was observed. In addition, the role of the electrolyte-nanorod interface was examined. It was observed that the lithiation of Si nanorods is dominated by surface diffusion. Upon the delithiation process, partial decomposition of Li(22)Si(5) particles was observed which can explain the irreversible capacity loss that is generally seen in Si anodes. This study shows that the radial straining due to lithiation does not cause cracking in nanorods as small in diameter as 26 nm, whereas cracks were observed during the lithiation of 55 nm Si nanorods.

Chitosan nanoparticle based delivery systems for sustainable agriculture

Development of technologies that improve food productivity without any adverse impact on the ecosystem is the need of hour. In this context, development of controlled delivery systems for slow and sustained release of agrochemicals or genetic materials is crucial. Chitosan has emerged as a valuable carrier for controlled delivery of agrochemicals and genetic materials because of its proven biocompatibility, biodegradability, non-toxicity, and adsorption abilities. The major advantages of encapsulating agrochemicals and genetic material in a chitosan matrix include its ability to function as a protective reservoir for the active ingredients, protecting the ingredients from the surrounding environment while they are in the chitosan domain, and then controlling their release, allowing them to serve as efficient gene delivery systems for plant transformation or controlled release of pesticides. Despite the great progress in the use of chitosan in the area of medical and pharmaceutical sciences, there is still a wide knowledge gap regarding the potential application of chitosan for encapsulation of active ingredients in agriculture. Hence, the present article describes the current status of chitosan nanoparticle-based delivery systems in agriculture, and to highlight challenges that need to be overcome.

Direct Compressive Measurements of Individual Titanium Dioxide Nanotubes

The mechanical compressive properties of individual thin-wall and thick-wall TiO(2) nanotubes were directly measured for the first time. Nanotubes with outside diameters of 75 and 110 nm and wall thicknesses of 5 and 15 nm, respectively, were axially compressed inside a 400 keV high-resolution transmission electron microscope (TEM) using a new fully integrated TEM-atomic force microscope (AFM) piezo-driven fixture for continuous recording of the force-displacement curves. Individual nanotubes were directly subjected to compressive loading. We found that the Youngs modulus of titanium dioxide nanotubes depended on the diameter and wall thickness of the nanotube and is in the range of 23-44 GPa. The thin-wall nanotubes collapsed at approximately 1.0 to 1.2 microN during axial compression.

Use of nanoparticles for controlled release of biocides in solid wood

The fungicides tebuconazole and chlorothalonil were successfully incorporated into polymeric nanoparticles with median particle diameters of 100–250 nm. Polyvinylpyridine (PVPy) and polyvinylpyridine-co-styrene (10% styrene and 30% styrene) were employed as the polymer matrix. The size of the nanoparticle increased with increased styrene content. The biocide also affected particle size, with chlorothalonil consistently yielding larger nanoparticles than tebuconazole. The release of the biocides from the polymeric nanoparticles was studied by suspending them in water. The release rate of both tebuconazole and chlorothalonil decreased with increased styrene content in the matrix, and chlorothalonil consistently released more slowly from the polymeric nanoparticles than did tebuconazole. It was found that biocides were successfully introduced into solid wood by incorporating them within polymeric nanoparticles, suspending the nanoparticles in water, and using the suspension to treat the wood with conventional pressure treatments. Once in the wood, the polymer matrix serves as a reservoir for the biocide and controls its release rate into the wood. Southern pine sapwood samples were treated with biocide-containing nanoparticles suspended in water, then exposed to the wood decay fungus Gloeophyllum trabeum using a simple wafer test. Samples exhibited fungal resistance at appropriate levels of biocide incorporation.

A morphological investigation of thermosets toughened with novel thermoplastics. I. Bismaleimide modified with hyperbranched polyester

The morphology of a bismaleimide (BMI) toughened with a thermoplastic hyperbranched aliphatic polyester (HBP) was studied by scanning electron microscopy (SEM). The effect of thermoplastic architecture, molecular weight, and end group on the size and arrangement of the dispersed phase was investigated and compared with the thermoset fracture toughness. SEM micrographs showed that higher molecular weight HBP formed roughly spherical dispersed domains of up to ∼ 60 μm, which contained BMI inclusions. Lower molecular weight HBP formed spherical dispersed thermoplastic domains, with diameters up to ∼ 10 μm with no BMI inclusions. A low molecular weight linear polyester with a repeat unit structure, which was similar to that of the HBP, was prepared and used as a control. Within error, BMI toughened with the linear control yielded the same fracture toughness as the best values obtained with HBP-modified BMI, but the morphology differed. The linear polyester phase separated into particles with a larger average diameter and also possessed some phase-inverted regions. End group effects were studied by modifying the hydroxy-terminated HBP to unreactive nitrophenyl, phenyl, and acetyl end groups. The nitrophenyl-terminated HBP did not phase separate from the thermoset, whereas the nonpolar phenyl- and acetyl-terminated HBP phase separated to form small (≤1 μm and ∼ 2 μm, respectively) spherical domains. Some comparisons were made to other results with HBP thermoplastics in BMI and epoxy thermosets.

Real-time observation of lithium fibers growth inside a nanoscale lithium-ion battery

Formation of lithium dendrite/fibers during charging-discharging cycles not only causes short circuit but is also known as a major safety issue. In this work, an electrochemical cell was constructed inside a transmission electron microscope to observe the real-time nucleation and growth of the lithium fibers inside a nanoscale Li-ion battery. Our results show that during the lithiation process, the lithium ions nucleate at the interface of anode and electrolyte and then grow into fibers. These fibers grew parallel to the direction of the applied electric field. Such observations can assist the nanoscale design of better electrodes and electrolyte materials needed for safe and high power Li-ion batteries.

Chemical and nanomechanical analysis of rice husk modified by ATRP-grafted oligomer

Rice husk (RH), an abundant agricultural residue, was reacted with 2-bromoisobutyryl bromide, to convert it to a heterogeneous polyfunctional macroinitiator for Atom Transfer Radical Polymerization (ATRP). The number of active sites placed on the RH surface was small, but they were ATRP active. Non-polar methyl methacrylate (MMA) and polar acrylonitrile (AN) were polymerized from the RH, and a sequential monomer addition was used to prepare an amphiphilic PMMA-b-PAN copolymer on RH surface. FTIR qualitatively confirmed the grafting. Gravimetric and XPS analysis of the different RH surface compositions indicated thin layers of oligomeric PMMA, PAN, and PMMA-b-PAN. The modified surfaces were mapped by nanomechanical AFM to measure surface roughness, and adhesion and moduli using the Derjaguin-Muller-Toropov model. RH grafted with MMA possessed a roughness value of 7.92, and a hard and weakly adhering surface (13.1 GPa and 16.7 nN respectively) while RH grafted with AN yielded a roughness value of 29 with hardness and adhesion values of 4.0 GPa and 23.5 nN. The PMMA-b-PAN modification afforded a surface with a roughness value of 51.5 nm, with hardness and adhesion values of 3.0 GPa and 75.3 nN.

Investigation of readily processable thermoplastic-toughened thermosets. II. Epoxy toughened using a reactive solvent approach

The fracture toughness of epoxy thermosets was increased by up to 220% using very low-molecular-weight (∼ 1000 g/mol) imide thermoplastic. The objective was to produce a low-viscosity prepolymer that could be easily autoclave-processed to give a tough thermoset. Here, an homogenous epoxy prepolymer was prepared by first synthesizing very low-molecular-weight linear aromatic imide (∼ 1000 g/mol) directly in a liquid allyl phenol reactive solvent, followed by dissolution of the epoxy (Epon® 825) and the cure agent (DDS) directly in the thermoplastic solution. The allyl phenol both cures into the epoxy network, through phenol functional groups, and accelerates the cure. The viscosity of the pure epoxy was 1.4 Pa S at 30°C. The prepolymer formulations ranged from ∼ 5-33 Pa S at 30°C, but all reduced to less than 1 Pa.S at 90°C. The onset of cure is well above 90°C so the prepolymer viscosity is within the range for autoclave processing. The cured resin plaques were not transparent, but phase-separated domains were not found by scanning electron microscopy, indicating that the domain size is below the detection limit of the instrument. The reactive solvent causes a decrease in both the T g and the high temperature modulus of the thermoset. Introduction of the thermoplastic results in partial recovery of the T g and modulus.

Magneto-photonic crystal optical sensors with sensitive covers

We report on a magneto-photonic crystal on-chip optical sensor for specific analyte detection with polypyrrole and gold nano particles as modified photonic crystal waveguide cover layers. The reaction of the active sensor material with various analytes modifies the electronic structure of the sensor layer causing changes in its refractive index and a strong transduction signal. Magneto-photonic crystal enhanced polarization rotation sensitive to the nature of the cover layer detects the index modification upon analyte adsorption. A high degree of selectivity and sensitivity are observed for aqueous ammonia and methanol with polypyrrole and for thiolated-gold- with gold-nanoparticles covers.

A study on the modulation of the electrical transport by mechanical straining of individual titanium dioxide nanotube

We report here, the deformation driven modulation of the electrical transport properties of an individual TiO2 nanotube via in situ transmission electron microscopy (TEM) using a scanning tunneling microscopy system. The current-voltage characteristics of each individual TiO2 nanotube revealed that under bending deformation within the elastic limit, the electrical conductivity of a TiO2 nanotube can be enhanced. High resolution TEM and electron diffraction pattern reveal that TiO2 nanotubes have tetragonal structure (a=0.378 nm, c=0.9513 nm, I41/amd). Analysis based on a metal-semiconductor-metal model suggests that in-shell, surface defect-driven conduction modes and electron–phonon coupling effect are responsible for the modulated semiconducting behaviors.