Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites

Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries.

Thermoplastic Polymer Nanocomposites Based on Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes

Using inorganic fullerene-like (IF) nanoparticles and inorganic nanotubes (INT) in organic-inorganic hybrid composite, materials provide the potential for improving thermal, mechanical, and tribological properties of conventional composites. The processing of such high-performance hybrid thermoplastic polymer nanocomposites is achieved via melt-blending without the aid of any modifier or compatibilizing agent. The incorporation of small quantities (0.1-4 wt.%) of IF/INTs (tungsten disulfide, IF-WS2 or molybdenum disulfide, MoS2) generates notable performance enhancements through reinforcement effects and excellent lubricating ability in comparison with promising carbon nanotubes or other inorganic nanoscale fillers. It was shown that these IF/INT nanocomposites can provide an effective balance between performance, cost effectiveness, and processability, which is of significant importance for extending the practical applications of diverse hierarchical thermoplastic-based composites.

Influência do acabamento superficial no desempenho de lubrificantes de motor novos e usados em automóveis abastecidos com E22 e E100.

Superfícies anisotrópicas lisas e rugosas foram usadas para avaliar o efeito da rugosidade e da direção de acabamento na formação de MoS2 a partir de MoDTC em ensaios tribologicos lubrificados com óleos de motor completamente formulados. Igualmente foi avaliada a resposta de atrito de lubrificantes de motor usados em carros de passageiros e em testes de dinamômetro abastecidos com etanol (E100) e gasolina (E22). Encontrou-se que tanto a direção de acabamento quanto a rugosidade foram fundamentais na reação MoDTC - MoS2. A direção de acabamento influenciou na medida que carregamentos tangenciais geram respostas diferentes nos ensaios quando são realizados paralelos e perpendiculares às linhas de acabamento, dado que para os últimos apresenta-se maior deformação plástica das asperezas, o qual favorece a obtenção de superfícies livres de óxidos, que tem sido indicada como uma condição necessário para que aconteça a reação MoDTC - MoS2. Por esta razão os valores de coeficiente de atrito próprios da formação de MoS2 foram obtidos somente nas superfícies rugosas ensaiadas perpendiculares às marcas de acabamento. Para superfícies com valores de índice de plasticidade superiores a 1 e nos quais não são formados filmes com boas capacidades redutoras de atrito, como é o caso de ensaios realizados com óleos base (livres de aditivos), o coeficiente de atrito não depende da rugosidade e da direção de acabamento. Nos ensaios lubrificados com óleos usado, encontraram-se valores de coeficiente de atrito similares aos obtidos nas condições de lubrificação com óleo livres de aditivos, devido provavelmente à redução do MoDTC no lubrificante como tem sido identificado por diferentes autores. Quando foram comparados os óleos usados contaminados com etanol com os óleos usados contaminados com gasolina, encontrou-se maior oxidação nestes últimos. Mesmo que estas diferenças de oxidação dos óleos não significaram diferenças em termos de atrito, estas podem ser importantes na medida em que óleos mais oxidados podem favorecer o desgaste oxidativo.

Large spin splitting in the conduction band of transition metal dichalcogenide monolayers

We study the conduction band spin splitting that arises in transition metal dichalcogenide (TMD) semiconductor monolayers such as MoS2, MoSe2, WS2, and WSe2 due to the combination of spin-orbit coupling and lack of inversion symmetry. Two types of calculation are done. First, density functional theory (DFT) calculations based on plane waves that yield large splittings, between 3 and 30 meV. Second, we derive a tight-binding model that permits to address the atomic origin of the splitting. The basis set of the model is provided by the maximally localized Wannier orbitals, obtained from the DFT calculation, and formed by 11 atomiclike orbitals corresponding to d and p orbitals of the transition metal (W, Mo) and chalcogenide (S, Se) atoms respectively. In the resulting Hamiltonian, we can independently change the atomic spin-orbit coupling constant of the two atomic species at the unit cell, which permits to analyze their contribution to the spin splitting at the high symmetry points. We find that—in contrast to the valence band—both atoms give comparable contributions to the conduction band splittings. Given that these materials are most often n-doped, our findings are important for developments in TMD spintronics.

Analysis of minerals from Arctic Ocean sediments

The Arctic Ocean System is a key player regarding the climatic changes of Earth. Its highly sensitive ice Cover, the exchange of surface and deep water masses with the global ocean and the coupling with the atmosphere interact directly with global climatic changes. The output of cold, polar water and sea ice influences the production of deep water in the North Atlantic and controls the global ocean circulation ("the conveyor belt"). The Arctic Ocean is surrounded by the large Northern Hemisphere ice sheets which not only affect the sedimentation in the Arctic Ocean but also are supposed to induce the Course of glacials and interglacials. Terrigenous sediment delivered from the ice sheets by icebergs and meltwater as well as through sea ice are major components of Arctic Ocean sediments. Hence, the terrigenous content of Arctic Ocean sediments is an outstanding archive to investigate changes in the paleoenvironment. Glazigenic sediments of the Canadian Arctic Archipelago and surface samples of the Arctic Ocean and the Siberian shelf regions were investigated by means of x-ray diffraction of the bulk fraction. The source regions of distinct mineral compositions were to be deciphered. Regarding the complex circumpolar geology stable christalline shield rocks, active and ancient fold belts including magmatic and metamorphic rocks, sedimentary rocks and wide periglacial lowlands with permafrost provide a complete range of possible mineral combinations. Non- glaciated shelf regions mix the local input from a possible point source of a particular mineral combination with the whole shelf material and function as a sampler of the entire region draining to the shelf. To take this into account, a literature research was performed. Descriptions of outcropping lithologies and Arctic Ocean sediments were scanned for their mineral association. The analyses of glazigenic and shelf sediments yielded a close relationship between their mineral composition and the adjacent source region. The most striking difference between the circumpolar source regions is the extensive outcrop of carbonate rocks in the vicinity of the Canadian Arctic Archipelago and in N Greenland while siliciclastic sediments dominate the Siberian shelves. In the Siberian shelf region the eastern Kara Sea and the western Laptev Sea form a destinct region defined by high smectite, (clino-) pyroxene and plagioclase input. The source of this signal are the extensive outcrops of the Siberian trap basalt in the Putorana Plateau which is drained by the tributaries of the Yenissei and Khatanga. The eastern Laptev Sea and the East Siberian Sea can also be treated as one source region containing a feldspar, quartz, illite, mica, and chlorite asscciation combined with the trace minerals hornblende and epidote. Franz Josef Land provides a mineral composition rich in quartz and kaolinite. The diverse rock suite of the Svalbard archipelago distributes specific mineral compositions of highly metamorphic christalline rocks, dolomite-rich carbonate rocks and sedimentary rocks with a higher diagenetic potential manifested in stable newly built diagenetic minerals and high organic maturity. To reconstruct the last 30,000 years as an example of the transition between glacial and interglacial conditions a profile of sediment cores, recovered during the RV Polarstern" expedition ARK-VIIIl3 (ARCTIC '91), and additional sediment cores around Svalbard were investigated. Besides the mineralogy of different grain size fractions several additional sedimentological and organo-geochemical Parameterswere used. A detailed stratigraphic framework was achieved. By exploiting this data set changes in the mineral composition of the Eurasian Basin sediments can be related to climatic changes. Certain mineral compositions can even be associated with particular transport processes, e.g. the smectitel pyroxene association with sea ice transport from the eastern Kara Sea and the western Laptev Sea. Hence, it is possible to decipher the complex interplay between the influx of warm Atlantic waters into the Southwest of the Eurasian Basin, the waxing and waning of the Svalbard1Barents- Sea- and Kara-Sea-Ice-Sheets, the flooding of the Siberian shelf regions and the surface and deep water circulation. Until now the Arctic Ocean was assumed to be a rather stable System during the last 30,000 years which only switched from a completely ice covered situation during the glacial to seasonally Open waters during the interglacial. But this work using mineral assemblages of sediment cores in the vicinity of Svalbard revealed fast changes in the inflow of warm Atlantic water with the Westspitsbergen Current (< 1000 years), short periods of advances and retreats of the marine based Eurasian ice sheets (1000-3000 years), and short melting phases (400 years?). Deglaciation of the marine-based Eurasian and the land-based north American and Greenland ice sheets are not simultaneous. This thesis postulates that the Kara Sea Ice Sheet released an early meltwater signal prior to 15,000 14C years leading the Barents Sea Ice Sheet while the western land-based ice sheets are following later than 13,500 14C years. The northern Eurasian Basin records the shift between iceberg and sea-ice material derived from the Canadian Arctic Archipelago and N-Greenland and material transported by sea-ice and surface currents from the Siberian shelf region. The phasing of the deglaciation becomes very obvious using the dolomite and quartd phyllosilicate record. It is also supposed that the flooding of the Laptev Sea during the Holocene is manifested in a stepwise increase of sediment input at the Lomonosov Ridge between the Eurasian and Amerasian Basin. Depending on the strength of meltwater pulses from the adjacent ice sheets the Transpolar Drift can probably be relocated. These movements are traceable by the distribution of indicator minerals. Based on the outcome of this work the feasibility of bulk mineral determination can be qualified as excellent tool for paleoenvironmental reconstructions in the Arctic Ocean. The easy preparation and objective determination of bulk mineralogy provided by the QUAX software bears the potential to use this analyses as basic measuring method preceding more time consuming and highly specialised mineralogical investigations (e.g. clay mineralogy, heavy mineral determination).

Controlling Long-Range Ordered Self-assembly of Solid-Binding Peptide Monolayers on Atomically Flat Layered Materials

Thesis (Master's)--University of Washington, 2016-06

Three-dimensional nitrogen-doped graphene supported molybdenum disulfide nanoparticles as an advanced catalyst for hydrogen evolution reaction

An efficient three-dimensional (3D) hybrid material of nitrogen-doped graphene sheets (N-RGO) supporting molybdenum disulfide (MoS2) nanoparticles with high-performance electrocatalytic activity for hydrogen evolution reaction (HER) is fabricated by using a facile hydrothermal route. Comprehensive microscopic and spectroscopic characterizations confirm the resulting hybrid material possesses a 3D crumpled few-layered graphene network structure decorated with MoS2 nanoparticles. Electrochemical characterization analysis reveals that the resulting hybrid material exhibits efficient electrocatalytic activity toward HER under acidic conditions with a low onset potential of 112 mV and a small Tafel slope of 44 mV per decade. The enhanced mechanism of electrocatalytic activity has been investigated in detail by controlling the elemental composition, electrical conductance and surface morphology of the 3D hybrid as well as Density Functional Theory (DFT) calculations. This demonstrates that the abundance of exposed active sulfur edge sites in the MoS2 and nitrogen active functional moieties in N-RGO are synergistically responsible for the catalytic activity, whilst the distinguished and coherent interface in MoS 2 /N-RGO facilitates the electron transfer during electrocatalysis. Our study gives insights into the physical/chemical mechanism of enhanced HER performance in MoS2/N-RGO hybrids and illustrates how to design and construct a 3D hybrid to maximize the catalytic efficiency.

Q-switched Raman fiber laser with molybdenum disulfide-based passive saturable absorber

We demonstrate a Q-switched Raman fiber laser using molybdenum disulfide (MoS2) as a saturable absorber (SA). The SA is assembled by depositing a mechanically exfoliated MoS2 onto a fiber ferrule facet before it is matched with another clean ferrule via a connector. It is inserted in a Raman fiber laser cavity with a total cavity length of about 8km to generate a Q-switching pulse train operating at 1560.2 nm. A 7.7-km-long dispersion compensating fiber with 584 ps·nm?1km?1 of dispersion is used as a nonlinear gain medium. As the pump power is increased from 395mW to 422mW, the repetition rate of the Q-switching pulses can be increased from 132.7 to 137.4 kHz while the pulse width is concurrently decreased from 3.35μs to 3.03 μs. The maximum pulse energy of 54.3 nJ is obtained at the maximum pump power of 422mW. These results show that the mechanically exfoliated MoS2 SA has a great potential to be used for pulse generation in Raman fiber laser systems.

Influência da estratigrafia mecânica no desenvolvimento de falhas distensionais em bacias do tipo Rifte: contribuição da modelagem física

In the last decades, analogue modelling has been used in geology to improve the knowledge of how geological structures are nucleated, how they grow and what are the main important points in such processes. The use of this tool in the oil industry, to help seismic interpretations and mainly to search for structural traps contributed to disseminate the use of this tool in the literature. Nowadays, physical modelling has a large field of applications, since landslide to granite emplacement along shear zones. In this work, we deal with physical modelling to study the influence of mechanical stratifications in the nucleation and development of faults and fractures in a context of orthogonal and conjugated oblique basins. To simulate a mechanical stratigraphy we used different materials, with distinct physical proprieties, such as gypsum powder, glass beads, dry clay and quartz sand. Some experiments were run along with a PIV (Particle Image Velocimetry), an instrument that shows the movement of the particles to each deformation moment. Two series of experiments were studied: i) Series MO: We tested the development of normal faults in a context of an orthogonal (to the extension direction) basin. Experiments were run taking into account the change of materials and strata thickness. Some experiments were done with sintectonic sedimentation. We registered differences in the nucleation and growth of faults in layers with different rheological behavior. The gypsum powder layer behaves in a more competent mode, which generates a great number of high angle fractures. These fractures evolve to faults that exhibit a higher dip than when they cross less competent layers, like the one of quartz sand. This competent layer exhibits faulted blocks arranged in a typical domino-style. Cataclastic breccias developed along the faults affecting the competent layers and showed different evolutional history, depending on the deforming stratigraphic sequence; ii) Series MOS2: Normal faults were analyzed in conjugated sub-basins (oblique to the extension direction) developed in a sequence with and without rheological contrast. In experiments with rheological contrast, two important grabens developed along the faulted margins differing from the subbasins with mechanical stratigraphy. Both experiments developed oblique fault systems and, in the area of sub-basins intersection, faults traces became very curved.

Fabrication of sub-10 nm lamellar structures by solvent vapour annealing of block copolymers

Fabrication of nanoscale patterns through the bottom-up approach of self-assembly of phase-separated block copolymers (BCP) holds promise for nanoelectronics applications. For lithographic applications, it is useful to vary the morphology of BCPs by monitoring various parameters to make “from lab to fab” a reality. Here I report on the solvent annealing studies of lamellae forming polystyrene-blockpoly( 4-vinylpyridine) (PS-b-P4VP). The high Flory-Huggins parameter (χ = 0.34) of PS-b-P4VP makes it an ideal BCP system for self-assembly and template fabrication in comparison to other BCPs. Different molecular weights of symmetric PS-b-P4VP BCPs forming lamellae patterns were used to produce nanostructured thin films by spin-coating from mixture of toluene and tetrahydrofuran(THF). In particular, the morphology change from micellar structures to well-defined microphase separated arrangements is observed. Solvent annealing provides a better alternative to thermal treatment which often requires long annealing periods. The choice of solvent (single and dual solvent exposure) and the solvent annealing conditions have significant effects on the morphology of films and it was found that a block neutral solvent was required to realize vertically aligned PS and P4VP lamellae. Here, we have followed the formation of microdomain structures with time development at different temperatures by atomic force microscopy (AFM). The highly mobilized chains phase separate quickly due to high Flory-Huggins (χ) parameter. Ultra-small feature size (~10 nm pitch size) nanopatterns were fabricated by using low molecular weight PSb- P4VP (PS and P4VP blocks of 3.3 and 3.1 kg mol-1 respectively). However, due to the low etch contrast between the blocks, pattern transfer of the BCP mask is very challenging. To overcome the etch contrast problem, a novel and simple in-situ hard mask technology is used to fabricate the high aspect ratio silicon nanowires. The lamellar structures formed after self-assembly of phase separated PS-b-P4VP BCPs were used to fabricate iron oxide nanowires which acted as hard mask material to facilitate the pattern transfer into silicon and forming silicon nanostructures. The semiconductor and optical industries have shown significant interest in two dimensional (2D) molybdenum disulphide (MoS2) as a potential device material due to its low band gap and high mobility. However, current methods for its synthesis are not ‘fab’ friendly and require harsh environments and processes. Here, I also report a novel method to prepare MoS2 layered structures via self-assembly of a PS-b-P4VP block copolymer system. The formation of the layered MoS2 was confirmed by XPS, Raman spectroscopy and high resolution transmission electron microscopy.

Multiscale Analysis for Field-Effect Penetration through Two-Dimensional Materials

Gate-tunable two-dimensional (2D) materials-based quantum capacitors (QCs) and van der Waals heterostructures involve tuning transport or optoelectronic characteristics by the field effect. Recent studies have attributed the observed gate-tunable characteristics to the change of the Fermi level in the first 2D layer adjacent to the dielectrics, whereas the penetration of the field effect through the one-molecule-thick material is often ignored or oversimplified. Here, we present a multiscale theoretical approach that combines first-principles electronic structure calculations and the Poisson–Boltzmann equation methods to model penetration of the field effect through graphene in a metal–oxide–graphene–semiconductor (MOGS) QC, including quantifying the degree of “transparency” for graphene two-dimensional electron gas (2DEG) to an electric displacement field. We find that the space charge density in the semiconductor layer can be modulated by gating in a nonlinear manner, forming an accumulation or inversion layer at the semiconductor/graphene interface. The degree of transparency is determined by the combined effect of graphene quantum capacitance and the semiconductor capacitance, which allows us to predict the ranking for a variety of monolayer 2D materials according to their transparency to an electric displacement field as follows: graphene > silicene > germanene > WS2 > WTe2 > WSe2 > MoS2 > phosphorene > MoSe2 > MoTe2, when the majority carrier is electron. Our findings reveal a general picture of operation modes and design rules for the 2D-materials-based QCs.

Electric Field Effects on Graphene Materials

Understanding the effect of electric fields on the physical and chemical properties of two-dimensional (2D) nanostructures is instrumental in the design of novel electronic and optoelectronic devices. Several of those properties are characterized in terms of the dielectric constant which play an important role on capacitance, conductivity, screening, dielectric losses and refractive index. Here we review our recent theoretical studies using density functional calculations including van der Waals interactions on two types of layered materials of similar two-dimensional molecular geometry but remarkably different electronic structures, that is, graphene and molybdenum disulphide (MoS2). We focus on such two-dimensional crystals because of they complementary physical and chemical properties, and the appealing interest to incorporate them in the next generation of electronic and optoelectronic devices. We predict that the effective dielectric constant (ε) of few-layer graphene and MoS2 is tunable by external electric fields (E ext). We show that at low fields (E ext < 0.01 V/Å) ε assumes a nearly constant value ∼4 for both materials, but increases at higher fields to values that depend on the layer thickness. The thicker the structure the stronger is the modulation of ε with the electric field. Increasing of the external field perpendicular to the layer surface above a critical value can drive the systems to an unstable state where the layers are weakly coupled and can be easily separated. The observed dependence of ε on the external field is due to charge polarization driven by the bias, which show several similar characteristics despite of the layer considered. All these results provide key information about control and understanding of the screening properties in two-dimensional crystals beyond graphene and MoS2

Device Physics of Two-Dimensional Crystalline Materials

Thesis (Ph.D.)--University of Washington, 2016-07

Spin injection in two-dimensional layered materials and local magnetoresistance side-effects

180 p.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.