Publications

Uranium is a high-value energy element, yet also poses an appreciable environmental burden. The demand for a straightforward, low energy, and environmentally friendly method for encapsulating uranium species can be beneficial for long-term storage of spent uranium fuel and a host of other applications. Leveraging on the low melting point (60 °C) of uranyl nitrate hexahydrate and nanocapillary effect, a uranium compound is entrapped in the hollow core of WS₂ nanotubes. Followingly, the product is reduced at elevated temperatures in a hydrogen atmosphere. Nanocrystalline UO₂ nanoparticles anchor within the WS₂ nanotube lumen are obtained through this procedure. Such methodology can find utilization in the processing of spent nuclear fuel or other highly active radionuclides as well as a fuel for deep space missions. Moreover, the low melting temperatures of different heavy metal-nitrate hydrates, pave the way for their encapsulation within the hollow core of the WS₂ nanotubes, as demonstrated herein.

WS₂ nanotubes present many new technologies under development, including reinforced biocompatible polymers, membranes, photovoltaic-based memories, ferroelectric devices, etc. These technologies depend on the aspect ratio (length/diameter) of the nanotubes, which was limited to 100 or so. A new synthetic technique is presented, resulting in WS₂ nanotubes a few hundred micrometers long and diameters below 50 nm (aspect ratios of 2000-5000) in high yields. Preliminary investigation into the mechanistic aspects of the two-step synthesis reveals that W₅O₁₄ nanowhisker intermediates are formed in the first step of the reaction instead of the ubiquitous W₁₈O₄₉ nanowhiskers used in the previous syntheses. The electrical and photoluminescence properties of the long nanotubes were studied. WS₂ nanotube-based paper-like material was prepared via a wet-laying process, which could not be realized with the 10 μm long WS₂ nanotubes. Ultrafiltration of gold nanoparticles using the nanotube-paper membrane was demonstrated.

Surface modification of tungsten disulfide (WS₂) nanoparticles (NPs) by a photo-initiator (PI) for radical curing of acrylate nano-structured systems has been studied with the purpose of acquiring covalent bonding of the acrylate matrix to the NPs surface. This surface functionalization was expected to photosensitize both the PI and the NPs thereby enhance the photocuring of the acrylate as well as improving its mechanical properties. The studied PI was the commonly used Bis(acyl) phosphane oxides (BAPOs). For surface modification of the WS₂ NPs, the BAPO was functionalized first with Tri(methoxy) silane (TMESI) to yield TMESI-BAPO moieties. Subsequently, the functionalized BAPO was chemisorbed to the WS₂ NPs resulting in WS₂ NPs surface modified by TMESI-BAPO pendant moieties. The functionalization and surface modification were confirmed using spectroscopic techniques as well as electron microscopy, and thermal measurements. Thermal gravimetric analysis (TGA) displayed 40 wt% weight loss for TMESI-BAPO modified WS₂ upon heating to 400 °C. The modified WS₂ NPs were incorporated into acrylate resin to study the curing kinetics and resulting mechanical properties compared to neat WS₂. Nanostructured acrylate with TEMSI-BAPO modified WS₂ NPs exhibited an increase of 83% in storage modulus and toughness compared to neat acrylate.

The effect of semiconducting tungsten disulfide (WS₂) nanoparticles (NPs), functionalized by either methacryloxy, glycidyl, vinyl, or amino silanes, has been studied in photocuring of acrylate and epoxy resins (the latter photocured according to a cationic mechanism). The curing time, degree of curing (DC), thermal effects, and mechanical properties of the radiation-cured resins were investigated. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses confirmed that a silane coating was formed (1\u20134 nm) on the NPs\u2019 surface having a thickness of 1\u20134 nm. Fourier transition infrared (FTIR) was used to determine the DC of the nanocomposite resin. The curing time of the epoxy resin, at 345\u2013385 nm wavelength, was 10 to 20 s, while for acrylate, the curing time was 7.5 min, reaching 92% DC in epoxy and 84% in acrylate. The glass transition temperature (Tg) of the photocured acrylates in the presence of WS₂ NPs increased. In contrast to the acrylate, the epoxy displayed no significant variations of the Tg. It was found that the silane surface treatments enhanced the DC. Significant increases in impact resistance and enhancement in shear adhesion strength were observed when the NPs were treated with vinyl silane. A previous study has shown that the addition of WS₂ NPs at a concentration of 0.5 wt.% is the optimal loading for improving the resin\u2019s mechanical properties. This study supports these earlier findings not only for the unmodified NPs but also for those functionalized with silane moieties. This study opens new vistas for the photocuring of resins and polymers in general when incorporating WS₂ NPs.

The radiation curing paradigm of opaque WS₂ nanoparticle (NP)-based epoxy/acrylate nanocomposites was studied and found to exhibit both a reduction in viscosity and an enhanced degree of curing when incorporating WS₂ NPs. The objective of this study was to investigate the mechanical, thermal, and physical properties of a radiation-induced and cured epoxy/acrylate blend containing 0.3 to 1.0 wt.% WS₂ NPs. Experimental results indicate that the tensile toughness increased by 22% upon optimizing the NP content compared to that of WS₂-free formulations. Tensile fractured surfaces with different WS₂ NP contents were analyzed with a scanning electron microscope and an atomic force microscope and showed distinctive morphology depending on the WS₂ NP content, supporting the results of the tensile test. The energy required to break shear adhesion specimens demonstrated an increase of up to 60% compared to that of the neat resin. The glass transition temperature determined by dynamic mechanical analysis presented similar or higher values upon WS₂ NP incorporation. Furthermore, up to 80% improvement in impact strength was demonstrated when WS₂ NPs were dispersed in the epoxy/acrylate blend. It was concluded that the surface chemistry and dispersion level of the WS₂ NPs are the major variables affecting the macro properties of cationically radiation-cured resins and their adhesion properties. This study is the first to demonstrate the possibility for radiation-induced curing of opaque NPs based on WS₂ that serve as both a reinforcement nanoparticle at low concentrations and an enhancement of the degree of curing.

Even though WS₂nanotubes (NTs-WS₂) have great potential as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) thanks to their unusual layered structure, their conductivity and cycling stability are far from satisfactory. To tackle these issues, carbon-coated WS₂(NTs-WS₂@C) nanocomposites were prepared through a facile synthesis method that involved precipitating a carbon precursor (20% sucrose) on WS₂nanotubes, followed by annealing treatment under an argon environment. Thanks to the presence of highly conductive and mechanically robust carbon on the outer surface, NTs-WS₂@C nanocomposites show improved electrochemical performance compared with bare NTs-WS₂. After 60 cycles at 80 mA g^-1current density, the cells display high capacities of 305 mAh g^-1in LIBs and 152 mAh g^-1in SIBs, respectively. As the current density increases to 600 mA g^-1, it provides specific capacities of 209 and 115 mAh g^-1, correspondingly. The enhanced electrochemical performance in LIBs and SIBs is primarily attributed to the synergistic effects of the tubular architecture of WS₂, carbon network and stable nanocomposite structure, which can effectively constrain volume variation during the metal ions intercalation/deintercalation processes.

Nanotubes of transition metal dichalcogenides such as WS2 and MoS2 offer unique quasi-1D properties and numerous potential applications. Replacing sulfur by selenium would yield ternary WS2(1\u2013x)Se2x (0 ≤ x ≤ 1; WSSe) nanotubes, which are expected to reveal strong modulation in their absorption edge as a function of selenium content, x Se. Solid WO2.72 oxide nanowhiskers were employed as a sacrificial template to gain a high yield of the nanotubes with a rather uniform size distribution. Though sulfur and selenium belong to the same period, their chemical reactivity with oxide nanowhiskers differed appreciably. Here, the closed ampoule technique was utilized to achieve the completion of the solid\u2013vapor reaction in short time scales instead of the conventional flow reactor method. The structure and chemical composition of the nanotubes were analyzed in detail. X-ray and electron diffractions indicated a systematic modulation of the WSSe lattice upon increasing the selenium content. Detailed chemical mapping showed that the sulfur and selenium atoms are distributed in random positions on the anion lattice site of the nanotubes. The optical excitonic features and absorption edges of the WSSe nanotubes do not vary linearly with the composition x Se, which was further confirmed by density functional theory calculations. The WSSe nanotubes were shown to exhibit strong light\u2013matter interactions forming exciton\u2013polariton quasiparticles, which was corroborated by finite-difference time-domain simulations. Transient absorption analysis permitted following the excited state dynamics and elucidating the mechanism of the strong coupling. Thus, nanotubes of the ternary WSSe alloys offer strong band gap tunability, which would be useful for multispectral vision devices and other optoelectronic applications.

Exploring the behavior of nanocrystals with varying shapes and sizes under high pressure is crucial to understanding the relationship between the morphology and properties of nanomaterials. In this study, we investigated the compression behaviors of WS2 nanotubes (NT−WS2) and fullerene-like nanoparticles (IF−WS2) by in situ high-pressure X-ray diffraction (XRD) and Raman spectroscopy. It was found that the bulk modulus of NT−WS2 is (81.7 GPa), which is approximately twice as large as that of IF-WS2 (46.3 GPa). This might be attributed to the fact that IF−WS2 with larger d-spacing along the c−axis and higher defect density are more compressible under isotropic pressure than NT−WS2. Thus, the slender NT−WS2 possess a more stable crystal structure than the IF-WS2. Our findings reveal that the effects of morphology and size play crucial roles in determining the high-pressure properties of WS2 nanoparticles, and provide significant insight into the relationship between structure and properties.

Misfit layered compounds (MLCs) MX-TX2, where M, T = metal atoms and X = S, Se, or Te, and their nanotubes are of significant interest due to their rich chemistry and unique quasi-1D structure. In particular, LnX-TX2 (Ln = rare-earth atom) constitute a relatively large family of MLCs, from which nanotubes have been synthesized. The properties of MLCs can be tuned by the chemical and structural interplay between LnX and TX2 sublayers and alloying of each of the Ln, T, and X elements. In order to engineer them to gain desirable performance, a detailed understanding of their complex structure is indispensable. MLC nanotubes are a relative newcomer and offer new opportunities. In particular, like WS2 nanotubes before, the confinement of the free carriers in these quasi-1D nanostructures and their chiral nature offer intriguing physical behavior. High-resolution transmission electron microscopy in conjunction with a focused ion beam are engaged to study SmS-TaS2 nanotubes and their cross-sections at the atomic scale. The atomic resolution images distinctly reveal that Ta is in trigonal prismatic coordination with S atoms in a hexagonal structure. Furthermore, the position of the sulfur atoms in both the SmS and the TaS2 sublattices is revealed. X-ray photoelectron spectroscopy, electron energy loss spectroscopy, and X-ray absorption spectroscopy are carried out. These analyses conclude that charge transfer from the Sm to the Ta atoms leads to filling of the Ta 5d z 2 level, which is confirmed by density functional theory (DFT) calculations. Transport measurements show that the nanotubes are semimetallic with resistivities in the range of 10\u20134 Ω·cm at room temperature, and magnetic susceptibility measurements show a superconducting transition at 4 K.

Analyzing naturally occurring layered alumo(magnesium)silicates (asbestos) minerals, Pauling proposed in 1930 that the strain in compounds with asymmetric structure, like kaolinite (hallyosite), lends itself for folding of the layers. Once transmission electron microscopy gained sufficient resolution in 1950, chrysotile and hallyosites nanotubes were discovered fully confirming this early hypothesis. Following the discovery of carbon fullerene (C₆₀) by Kroto and Smalley and carbon nanotubes by Iijima, Tenne proposed a new mechanism for the formation of nanotubes from inorganic compounds with layered structure via seaming of their chemically reactive rims. Early on, nanotubes of WS₂ and subsequently MoS₂, GaSe and BN were found experimentally and in silico and many others followed over the years. Here, different mechanisms for the formation of nanotubes from inorganic compounds with layered structure are analyzed with a few examples. Few potential applications of such nanotubes are briefly discussed, as well. Finally, several frontiers and scientific challenges in this field in the years ahead are presented

Misfit layered compounds (MLCs) have been studied in the literature for the last 40 years. They are generally made of an alternating sequence of two monolayers, a distorted rocksalt structure, and a hexagonal layered compound. In a typical MLC, the c-axis is common to the two monolayers and so is one of the axes in the layer plan. However, the two compounds are non-commensurate along at least one axis, and the ratio between the two axes is an irrational number making the MLC a non-stoichiometric compound. The two main families of MLC are those based on metal dichalcogenides and CoO2 as the hexagonal layered compound. Traditionally, ternary MLCs were prepared and studied, but some quaternary and multinary MLC minerals have been known for many years. Over the last few years, interest in MLCs with four and even larger number of atoms has grown. Doping or alloying of a ternary MLC permits precise control of the charge carrier density and hence the electrical, thermoelectric, catalytic, and optical properties of such compounds. In this short review, some of these developments will be discussed with the main emphasis put on quaternary MLC nanotubes belonging to the chalcogenide series. The synthesis, structural characterization, and some of their properties are considered. Some recent developments in quaternary cobaltite MLCs and recent studies on exfoliated MLCs are discussed as well.

The non-stoichiometric misfit layered compounds (MLC) of the general formula ((MX)(1+y))(m)(TX2)(n) (abbreviated herein as MX-TX2) have been investigated quite extensively over the last 30 years. Here MX is a atomic slab of a material with distorted rocksalt structure and TX2 is a layered compound with hexagonal (octahedral) coordination between the metal T atom and the chalcogen X atom. Recognizing the mismatch between the two (MX and TX2) sublattices, nanotubes from the MLC of different compositions were described in the past. In particular, semimetallic nanotubes belonging to the family LnX-TaX2 with Ln = rare earth atom and X = S, Se, Te have been studied in the past. While some of them, like LaS-TaS2 were obtained with moderately high yields, others like YbS-TaS2 were scarce. In the present study, a new strategy for promoting the yield of such MLC nanotubes by alloying the LaS sublattice with another Ln atom is proposed. Detailed transmission electron microscopy investigation of the (mixed) Ln(x)La((1-x))S-TaS2 (Ln = Pr, Sm, Ho, Yb) nanotubes show clearly that the substituting Ln atom resides in the rocksalt LaS sublattice of the nanotubes. Raman measurements show distinct differences between mixed tubes with open-shell (Pr, Sm, Ho) and close-shell (La, Yb) rare-earth atoms. Density functional calculations show that the interplay between two important factors determine the enhanced stability of the mixed nanotubes- the size and electronic structure of the substituting rare-earth atom. The smaller is the substituting rare-earth atom (larger Z number), the more dissimilar it is to the original La atom. This dissimilarity enhances the incommensurability between the Ln(x)La((1-x))5 and the TS2 subunits, promoting thereby the stability of the mixed MLC. However, the electronic structure of the Ln atom was found to play a more significant role. The MLC lattice of the LaS-TaS2 is electron-rich and consequently the 4d(z)(2) level of Ta is full. The unoccupied 4f levels of the substituent open-shell atoms (Pr, Sm, Ho), which are positioned below the Fermi level, serve as electron acceptors. Consequently, the Ln substitution is found to enhance the stability of the mixed lattice and nanotubes thereof. This strategy can be employed for enhancing the yield of these and other misfit nanotubes using different substituents of the right size and energy profile.

Proton exchange membranes with high through-plane proton conductivity are a critical component of high-performance fuel cells, electrolyzers, and batteries. However, isotropically distributed proton-conducting channel structures of current membranes present a limitation. Herein, a proton exchange membrane with straight proton-conducting channels aligned in the thickness direction is fabricated, achieved by magnetic field-induced alignment of proton-conductive, paramagnetic, and one-dimensional (1D) tungsten disulfide nanotubes (pms-WS2) distributed in a perfluorinated sulfonic acid (Nafion) membrane. The pms-WS2 nanotubes feature straight WS2 nanotubes as a core, a polystyrenesulfonate (PSS) skin layer, and surface-decorated Fe3O4 nanoparticles. A molecular dynamics simulation suggests that straight proton-conducting channels are constructed at the interface of Nafion/pms-WS2 due to densely populated sulfonic acids. Spectroscopic investigation and magnetization measurements verify the through-plane alignment of pms-WS2 under a weak through-plane magnetic field (0.035 T) during the removal of solvent from the membrane cast. Compared with a recast Nafion membrane with the same thickness, the through-plane aligned composite membrane exhibits 69% higher proton conductivity and 51% higher power performance in a proton exchange membrane fuel cell, demonstrating its efficacy. The through-plane alignment of a proton-conductive inorganic 1D material promises improved power performance of advanced electrochemical devices.

We present the analysis of a family of nanotubes (NTs) based on the quaternary misfit layered compound (MLC) YxLa1-xS-TaS2. The NTs were successfully synthesized within the whole range of possible compositions via the chemical vapor transport technique. In-depth analysis of the NTs using electron microscopy and spectroscopy proves the in-phase (partial) substitution of La by Y in the (La,Y)S subsystem and reveals structural changes compared to the previously reported LaS-TaS2 MLC-NTs. The observed structure can be linked to the slightly different lattice parameters of LaS and YS. Raman spectroscopy and infrared transmission measurements reveal the tunability of the plasmonic and vibrational properties. Density-functional theory calculations showed that the YxLa1-xS-TaS2 MLCs are stable in all compositions. Moreover, the calculations indicated that substitution of La by Sc atoms is electronically not favorable, which explains our failed attempt to synthesize these MLC and NTs thereof.

Core-shell nanoparticles provide a unique morphology to exploit electronic interactions between dissimilar materials, conferring upon them new or improved functionalities. MoS2 is a layered transition-metal disulfide that has been studied extensively for the hydrogen evolution reaction (HER) but still suffers from low electrocatalytic activity due to its poor electronic conductivity. To understand the fundamental aspects of the MoS2-Au hybrids with regard to their electrocatalytic activity, a single to a few layers of MoS2 were deposited over Au nanoparticles via a versatile procedure that allows for complete encapsulation of Au nanoparticles of arbitrary geometries. High-resolution transmission electron microscopy of the Au@MoS2 nanoparticles provides direct evidence for the core-shell morphology and also reveals the presence of morphological defects and irregularities in the MoS2 shell that are known to be more active for HER than the pristine MoS2 basal plane. Electrochemical measurements show a significant improvement in the HER activity of AugMoS(2) nanoparticles relative to freestanding MoS2 or Au-decorated MoS2. The best electrochemical performance was demonstrated by the Au nanostars-the largest Au core employed here-encapsulated in a MoS2 shell. Density-functional theory calculations show that charge transfer occurs from the Au to the MoS2 layers, producing a more conductive catalyst layer and a better electrode for electrochemical HER The strategies to further improve the catalytic properties of such hybrid nanoparticles are discussed.

Advanced nanomaterials play a prominent role in nanoscience and nanotechnology developments, opening new frontiers in these areas. Among these nanomaterials, due to their unique characteristics and enhanced chemical and physical properties, inorganic nanotubes have been considered one of the most interesting nanostructures. In recent years, important progress has been achieved in the production and study of these nanomaterials, including boron nitride, transition metal dichalcogenide nanotubular structures, misfit-based nanotubes and other hybrid/doped nanotubular objects. This review is devoted to the in-depth analysis of recent studies on the synthesis, atomic structures, properties and applications of inorganic nanotubes and related nanostructures. Particular attention is paid to the growth mechanism of these nanomaterials. This is a crucial point for the challenges ahead related to the mass production of high-quality defect-free nanotubes for a variety of applications.

Composites of poly(l-lactic acid) (PLLA) reinforced by adding inorganic nanotubes of tungsten disulfide (INT-WS2) were prepared by solvent casting. In addition to the pristine nanotubes, PLLA nanocomposites containing surface modified nanotubes were studied as well. Several surface-active agents, including polyethylene imine (PEI), were studied in this context. In addition, other biocompatible polymers, like poly d,l-lactic acid (PDLLA) and others were considered in combination with the INT-WS2. The nanotubes were added to the polymer in different proportions up to 3 wt %. The dispersion of the nanotubes in the nanocomposites were analyzed by several techniques, including X-ray tomography microscopy (Micro-XCT). Moreover, high-temperature rheological measurements of the molten polymer were conducted. In contrast to other nanoparticles, which lead to a considerable increase of the viscosity of the molten polymer, the WS2 nanotubes did not affect the viscosity significantly. They did not affect the complex viscosity of the molten PLLA phase, either. The mechanical and tribological properties of the nanocomposites were found to improve considerably by adding the nanotubes. A direct correlation was observed between the dispersion of the nanotubes in the polymer matrix and its mechanical properties.

Self-lubricating films are of immense importance in various tribological applications. Nanoparticles are often used as the lubricating component in such films. Inorganic fullerene-like (IF) nanoparticles of WS2 have been used in the past for variety of tribological applications including for self-lubricating polymer and metallic films. IF nanoparticles from MoS2 with superior tribological behavior were reported in the past. However, such nanoparticles, which are available in minute amounts, were not applied for self-lubricating coatings in the past. In the current work, inorganic fullerene-like nanoparticles of MoS2 (IF-MoS2) were co-evaporated with titanium (cobalt) on metal substrates. The films were characterized by different techniques and were shown to have good adhesion to the underlying substrate. Furthermore, tribological tests indicated that such coatings exhibit improved friction coefficient (roughly 0.1) and very small wear under relatively high load.

Herein, the use of highly concentrated sunlight for materials science research is reviewed. Specific research directions include: (1) the generation of inorganic nanostructures, some of which had eluded experimental realization with conventional synthetic processes, and (2) elucidating the processes governing the degradation of organic and perovskite-based photovoltaic materials and devices, along with accelerated assessment of their stability. Both approaches employ solar concentrators capable of producing flux densities exceeding those of terrestrial solar radiation by up to three orders of magnitude, and are geared toward either creating extensive ultrahot reactor conditions conducive to the rapid, safe synthesis of unusual nanomaterials or judiciously interrogating photovoltaic devices.

The synthesis and characterization of nanotubes from misfit layered compounds (MLCs) of the type (LnS)(1+y)TaS2 (denoted here as LnS-TaS2; Ln=Pr, Sm, Gd, and Yb), not reported before, are described (the bulk compound YbS-LaS2 was not previously documented). Transmission electron microscopy and selected area electron diffraction showed that the interlayer spacing along the c axis decreased with an increase in the atomic number of the lanthanide atom, which suggested tighter interaction between the LnS layer and TaS2 for the late lanthanides. The Raman spectra of the tubules were studied and compared to those of the bulk MLC compounds. Similar to the bulk MLCs, the Raman spectra could be divided into the low-frequency modes (110-150cm(-1)) of the LnS lattice and the high-frequency modes (250-400cm(-1)) of the TaS2 lattice. The Raman spectra indicated that the vibrational lattice modes of the strained layers in the tubes were stiffer than those in the bulk compounds. Furthermore, the modes of the late lanthanides were higher in energy than those of the earlier lanthanides, which suggested larger charge transfer between the LnS and TaS2 layers for the late lanthanides. Polarized Raman measurements showed the expected binodal intensity profile (antenna effect). The intensity ratio of the Raman signal showed that the E-2g mode of TaS2 was more sensitive to the light-polarization effect than its A(1g) mode. These nanotubes are expected to reveal interesting low-temperature quasi-1D transport behavior.

In this paper, we demonstrate the formation of hybrid nanostructures consisting of two distinctive components mainly in a one-to-one ratio. Thermolysis of inorganic nanotubes (INT) and closed-cage, inorganic fullerene-like (IF) nanoparticles decorated with a dense coating of metallic nanoparticles (M = Au, Ag, Pd) results in migration of relatively small NPs or surface-enhanced diffusion of atoms or clusters, generating larger particles (ripening). AuNP growth on the surface of INTs has been captured in real time using in situ electron microscopy measurements. Reaction of the AuNP-decorated INTs with an alkylthiol results in a chemically induced NP fusion process at room temperature. The NPs do not dissociate from the surfaces of the INTs and IFs, but for proximate IFs we observed fusion between AuNPs originating from different IFs.

Screening effect in finite-length carbon nanotubes (CNT) and their agglomerates hinders significantly the electromagnetic interaction in composite materials. Screening effect is strong in the microwave range, and it decreases with increasing frequency resulting in a strong frequency dependence of the effective conductivity of the composite. Since screening effect is rather small in the terahertz range, the effective conductivity in this range is determined directly by the intrinsic conductivity of the inclusions. The ratio of the microwave to terahertz effective conductivities was proposed as a parameter to estimate how effectively carbon nanotube inclusions contribute to the electromagnetic performance of composite materials in the microwave range. CNT film was considered as a material where maximal possible interaction of the CNTs with EM field occurs. Single-walled CNT films and CNT-based composite materials, as well as hybrid film comprising mixtures of WS
₂ nanotubes and CNTs were fabricated and measured in the microwave and terahertz ranges. The electromagnetic field interaction with the inclusions has been estimated for all the samples fabricated.

Inorganic fullerene-like closed-cage nanoparticles of MoS2 and WS2 (IF-MoS2; IF-WS2), are synthesized in substantial amounts and their properties are widely studied. Their superior tribological properties led to large scale commercial applications as solid lubricants in numerous products and technologies. Doping of these nanoparticles can be used to tune their physical properties. In the current work, niobium (Nb) doping of the nanoparticles is accomplished to an unprecedented low level (

We report here a new methodology for the formation of freestanding nanotubes composed of individual gold nanoparticles (NPs) cross-linked by coordination complexes or porphyrin molecules using WS
₂ nanotubes (INT-WS
₂) as a template. Our method consists of three steps: (i) coverage of these robust inorganic materials with monodispersed and dense monolayers of gold NPs, (ii) formation of a molecular AuNP network by exposing these decorated tubes to solutions containing a ruthenium polypyridyl complex or meso-tetra(4-pyridyl)porphyrin, and (iii) removal of the INT-WS
₂ template with a hydrogen peroxide solution. Nanoindentation of the template-free AuNP tubes with atomic force microscopy indicates a radial elastic modulus of 4 GPa. The template-free molecular AuNP tubes are characterized using scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-Raman spectroscopy. The methodology provides a convenient and scalable strategy for the realization of molecular AuNP tubes with a defined length and diameter, depending on the dimensions of the template.

The review concerns the development and the state-of-the-art in studies on the surface modification methods aimed at fabricating promising nanocomposites based on multilayer inorganic tubular and onion (fullerene-like) MoS2 and WS2 nanostructures. The synthetic details and structural features of these materials are considered. Considerable attention is paid to targeted functionalization of molybdenum and tungsten disulfide nanostructures and to fundamental principles that underlie their ability to chemical interactions. The functional properties and applications of the obtained materials are described.

Multi\u2010walled carbon (MWCNT) and tungsten disulfide (INT\u2010WS2) nanotubes are materials with excellent mechanical properties, high electrical and thermal conductivity. These special properties make them excellent candidates for high strength and electrically conductive polymer nanocomposite applications. In this work, the possibility of the improvement of mechanical, thermal and electrical properties of poly(trimethylene terephthalate) (PTT) by the introduction of MWCNT and INT\u2010WS2 nanotubes was investigated. The PTT nanocomposites with low loading of nanotubes were prepared by in situ polymerization method. Analysis of the nanocomposites' morphology carried out by SEM and TEM has confirmed that well\u2010dispersed nanotubes in the PTT matrix were obtained at low loading (

Recently, polyhedral; octahedral fullerene-like structures and cylindrical nanotubes of gallium sulfide have been produced in far from equilibrium conditions using a high power solar synthesis and Pb as growth promoter. Their exact atomistic structure and their formation path remain unknown. Here, the models of fullerenes and nanotubes are designed for both stable β- and metastable γ-polymorphs of GaS. Their stability and electronic properties were investigated as a function of both the morphology and size using density-functional tight-binding method. The results manifest that, construction principles for GaS fullerenes are different from those for \u201cclassical\u201d dichalcogenide fullerenes. In contrast to the bulk, the kinetic stability of fullerene-like structures of the γ-GaS phase is found to be larger, than that for β-GaS which is ascribed to a sterical specificity of intersected γ-GaS layers. We predict that, the γ-GaS phase should arise at least as an intermediate state during the synthesis of polyhedral GaS nanoparticles. Notwithstanding the polymorphic type, the size and the morphology of GaS nanostructures, they are all semiconductors. Finally, the possible composition and electronic properties of Pb||GaS interface within the Pb@GaS nanoparticles are discussed.

Owing to their unique properties such as mechanical, optical, magnetic, nanomaterials attracted a great interest over the last two decades. Inorganic nanotubes, e.g. WS2, make an important class of nanomaterials with numerous potential applications. In the current work, a new synthetic strategy is developed to decorate the surface of WS2 nanotubes with FeWO4 nanoparticles. The FeWO4 nanoparticles were produced by first depositing amorphous iron oxide film onto the WS2 nanotubes' surface and, subsequently, high-temperature annealing (600 C-degrees). Careful analysis by electron microscopy; X-ray diffraction and other techniques were carried out. Based on these analyses, the growth mechanism of the hybrid nanostructures was elucidated. Magnetic measurements were employed to shed light on the magnetic behavior of the hybrid nanostructures. The orientation and position of the WS2 nanotubes decorated with the FeWO4 nanoparticles could be partially affected by applying a magnetic field using non-viscous solvents, like ethanol.

Nanoparticles, and more specifically gold nanoparticles (AuNPs), have attracted much scientific and technological interest in the last few decades. Their popularity is attributed to their unique optical, catalytic, electrical and magnetic properties when compared with the bulk. However, one of the main problems with AuNPs is their long-term stability. Two-dimensional materials like MoS₂ (WS₂) are semiconductors that exhibit a combination of properties which make them suitable for electronic, optical and (photo)catalytic devices. Few-layer MoS₂ (WS₂) nanoparticles (NPs), and in particular single-layer ones, show intriguing optical and electrical properties which are very different from those of the bulk compounds. Here we demonstrate the synthesis of AuNPs sheathed by a single layer of MoS₂ (WS₂), i.e. a core-shell nanostructure (AuNP@1L-MoS₂). The hybrid NPs exhibit optical properties that are different from those of either constituent and are amenable for modulation via their chemistry, offering a myriad of applications.

New types of core-shell nanoparticles are reported: Pb@GaS fullerene-like and nanotubular structures, achieved via the continuously high reactor temperatures and ultra-hot strong-gradient annealing environments created by highly concentrated sunlight. Structural and chemical characterizations suggest a formation mechanism where vaporized Pb condenses into nanoparticles that are stabilized as they become covered by molten GaS, the ensuing crystallization of which creates the outer layers. Hollow-core GaS fullerene-like nanoparticles and nanotubes were also observed among the products, demonstrating that a single solar procedure can generate a variety of core-shell and hollow nanostructures. The proposed formation mechanisms can account for their relative abundance and the characterization data.

Inorganic fullerene (IF)-like nanoparticles and inorganic nanotubes (INT) form a relatively new class of nanomaterials. They are generically produced from layered (2D) materials, which enable formation of stable, closed, hollow structures in the nanodomain. Taking advantage of the structural analogy between graphite and inorganic 2D compounds, researchers demonstrated that nanoparticles of WS₂ (Tenne et al. 1992), MoS₂ (Feldman et al. 1995, Margulis et al. 1993), BN (Chopra et al. 1995, Golberg et al. 1998), NiCl₂ (Rosenfeld Hacohen et al. 1998), and the like become unstable in the platelet (bulk) form and spontaneously assemble into hollow seamless structures, such as multiwall quasi-spherical spheres, nanooctahedra (Parilla et al. 1999), or nanotubes. The research on these nanostructures brought about major advances in chemistry and nanotechnology, and pointed to many possible applications.

In this report, a systematic study of the effects of p- and n-type doping of the inorganic fullerene (IF) MoS₂ on the efficiency of the hydrogen evolution reaction (HER) is described. Active edge site enriched IF-MoS₂, promoted by strategically introducing Nb (p-type) and Re (n-type) dopants (below 500 ppm), enables facile HER over a range of pH values. Experimental results suggest that although Nb-doping on IF-MoS₂ leads to better electrocatalytic HER activity in an alkaline medium with an onset potential difference of 80 mV, Re-doping gives excellent activity in an acidic medium. The present work presents a systematic study of HER activity by finely tuning the activity in different electrolyte media with varied pH values through deliberate doping of the parent catalyst with p- and n- type materials. The doped IF-MoS₂ catalysts exhibit excellent catalytic activity even with sea water as an electrolyte.

The relationship between structure and properties has been followed for different nanoscale forms of tungsten disulfide (2H-WS₂) namely exfoliated monolayer and few-layer nanoplatelets, and nanotubes. The similarities and differences between these nanostructured materials have been examined using a combination of optical microscopy, scanning and high-resolution transmission electron microscopy and atomic force microscopy. Photoluminescence and Raman spectroscopy have also been used to distinguish between monolayer and few-layer material. Strain induced phonon shifts have been followed from the changes in the positions of the A_1g and E_2g¹ Raman bands during uniaxial deformation. This has been modelled for monolayer using density functional theory with excellent agreement between the measured and predicted behaviour. It has been found that as the number of WS₂ layers increases for few-layer crystals or nanotubes, the A_1g mode hardens whereas the E_2g¹ mode softens. This is believed to be due to the A_1g mode, which involves out of plane atomic movements, being constrained by the increasing number of WS₂ layers whereas easy sliding reduces stress transfer to the individual layers for the E_2g¹ mode, involving only in-plane vibrations. This finding has enabled the anomalous phonon shift behaviour in earlier pressure measurements on WS₂ to be resolved, as well as similar effects in other transition metal dichalcogenides, such as molybdenum disulfide, to be explained.

We present Raman spectra of misfit layer (PbS)(1.14)NbS2 nanotubes and lead intercalated NbS2 nanotubes. They represent interesting model systems to investigate the nature of interlayer interaction in layered materials. A direct correlation to the Raman modes of the parent 2H-NbS2 compound exists, but some modes are seen drastically upshifted in frequency in the misfit layer and intercalated compound while others remain almost unchanged. On the basis of the Raman spectroscopic investigations and with the help of supporting calculations we examine different interlayer bonding mechanisms and contribute to the discussion as to why these frequency shifts occur.

Polyvinyl alcohol (PVA) is a biocompatible, semi-crystalline and water soluble polymer with moderate tensile properties. To improve the thermal and mechanical properties of PVA, as well as to reduce water uptake, structural modification by glutaric acid (GA) and nanoparticle reinforcement by tungsten disulphide nanotubes (WSNTs) were used to prepare PVA based composites. We observed a significant drop in the water uptake of GA crosslinked PVA, an indication of the formation of a network. Fourier transform infrared spectroscopy was applied to confirm the presence of covalent bonds formed during the crosslinking. Crosslinked PVA and composites are found to have higher thermal stability and mechanical properties compared to their un-crosslinked counterparts. Tensile tests show that the presence of WSNTs increases the strength (up to 25%), modulus (up to 120%) and toughness (up to 80%) of the pristine as well as the crosslinked PVA. (C) 2016 Elsevier Ltd. All rights reserved.

The process engineering of Mg alloys is nevertheless compromised due to their relatively poor mechanical properties. To address some of these difficulties, metal-matrix composites (MMCs) of Mg-alloys have been investigated for sometime. In the present work, small amounts (up to 1 wt%) of WS2 nanotubes are mixed with Mg-alloy (AZ31) using melt-stirring process above 700 degrees C. The new MMC nano-composites exhibit much superior mechanical properties vis a vis the pristine alloy. Metallographic investigation demonstrates that the average grain size has been reduced in inverse proportion to the added amounts of nanotubes up to 1 wt%. Physical considerations suggest that the main mechanism responsible for the reinforcement effect lies in the mismatch between the thermal expansion coefficients of the metal and the nanotubes. This mismatch induced large density of dislocations in the grain boundaries in the vicinity of the nanotube-matrix interface, which obstruct the crack propagation. (C) 2015 Elsevier B.V. All rights reserved.

Silica aerogels are unique solids with extremely high porosity (>99.5% air by volume), transparency and low density. With their high surface area and thermal resistivity they make excellent heat insulators. However, due to their fine structure they are fragile and therefore impractical for structural applications. To improve their mechanical properties we suggest incorporation of minute amounts of tungsten disulfide nanotubes. Nanotubes of tungsten disulfide are known for their high mechanical strength, strain and thermal stability. Adding some 0.1\u20131 wt% of tungsten disulfide nanotubes to a variety of polymers clearly lead to substantial improvement in their mechanical properties. The current study reports the preparation of silica aerogels compounded with small amounts of tungsten disulfide nanotubes. Three-point bending and uniaxial compression tests of the composite aerogel revealed 85% and 23% improvement in the composite material toughness, respectively.

The incorporation of nanostructures into nanoelectronic and nanoelectromechanical systems is a long sought-after goal. In the present article, we report the first torsional electromechanical measurements of pure inorganic nanotubes. The WS₂ nanotubes exhibited a complex and reproducible electrical response to mechanical deformation. We combined these measurements with density-functional-tight-binding calculations to understand the interplay between mechanical deformation, specifically torsion and tension, and electrical properties of WS₂ nanotubes. This yielded the understanding that the electrical response to mechanical deformation may span several orders of magnitude on one hand and detect several modes of mechanical deformation simultaneously on the other. These results demonstrate that inorganic nanotubes could thus be attractive building blocks for nanoelectromechanical systems such as highly sensitive nanometric motion sensors.

We report the synthesis and supporting density-functional-theory computations for a closed-cage, misfit layered-compound superstructure from PbS-SnS₂, generated by highly concentrated sunlight from a precursor mixture of Pb, SnS₂, and graphite. The unique reactor conditions created in our solar furnace are found to be particularly conducive to the formation of these nanomaterials. Detailed structural and chemical characterization revealed a spontaneous inside-out formation mechanism, with a broad range of nonhollow fullerene-like structures starting at a diameter of ∼20 nm and a wall thickness of ∼5 layers. The computations also reveal a counterintuitive charge transfer pathway from the SnS₂ layers to the PbS layers, which indicates that, in contrast to binary-layered compounds where it is principally van der Waals forces that hold the layers together, polar forces appear to be as important in stabilizing superstructures of misfit layered compounds. (Figure Presented).

Inorganic, fullerene-like (IF) nanoparticles of tungsten disulfide (WS2) and molybdenum disulfide (MoS2) have been synthesised in the past and their useful tribological properties have been studied quite extensively. Rhenium doping of such nanoparticles was also reported and studied to some extent. Herein, further studies of the physico-chemical properties are reported in connection to lubrication under mild loads. Due to their self-repelling character, the doped nanoparticles form tessellated monolayers on certain substrates. When mixed in small amounts, the IF nanoparticles lead to a reduction in the viscosity of water-based gels. Furthermore, the added nanoparticles lead to a precipitous reduction in traction force (friction) under mild loads. The lubrication mechanism of such nanoparticles is briefly discussed.

Impaired salivary gland (SG) function leading to oral diseases is relatively common with no adequate solution. Previously, tissue engineering of SG had been proposed to overcome this morbidity, however, not yet clinically available. Multiwall inorganic (tungsten disulfide [WS₂]) nanotubes (INT-WS₂) and fullerene-like nanoparticles (IF-WS₂) have many potential medical applications. A yet unexplored venue application is their interaction with SG, and therefore, our aim was to test the biocompatibility of INT/IF-WS₂ with the A5 and rat submandibular cells (RSC) SG cells. The cells were cultured and subjected after 1 day to different concentrations of INT-WS₂ and were compared to control groups. Growth curves, trypan blue viability test, and carboxyfluorescein succinimidyl ester (CFSE) proliferation assay were obtained. Furthermore, cells morphology and interaction with the nanoparticles were observed by light microscopy, scanning electron microscopy and transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy. The results showed no significant differences in growth curves, proliferation kinetics, and viability between the groups compared. Moreover, no alterations were observed in the cell morphology. Interestingly, TEM images indicated that the nanoparticles are uptaken by the cells and accumulate in cytoplasmic vesicles. These results suggest promising future medical applications for these nanoparticles.

Theoretical analysis of experimental data on unzipping multilayered WS ₂ nanotubes by consequent intercalation of lithium atoms and 1-octanethiol molecules [C. Nethravathi, et al., ACS Nano, 2013, 7, 7311] is presented. The radial expansion of the tube was described using continuum thin-walled cylinder approximation with parameters evaluated from ab initio calculations. Assuming that the attractive driving force of the 1-octanethiol molecule is its reaction with the intercalated Li ions ab initio calculations of a 1-octanethiol molecule bonding with Li⁺ were carried out. In addition, the non-chemical interactions of the 1-octanethiol dipole with an array of positive point charges representing Li⁺ were taken into account. Comparing between the energy gain from these interactions and the elastic strain energy of the nanotube allows us to evaluate a value for the tube wall deformation after the implantation of 1-octanethiol molecules. The ab initio molecular dynamics simulation confirmed our estimates and demonstrated that a strained WS₂ nanotube, with a decent concentration of 1-octanethiol molecules, should indeed be unzipped into the WS₂ nanoribbon.

In the present work, MoS2 nanoparticles with fullerene-like structure, and most particularly those doped with minute amounts of rhenium atoms, are used as additive to medical gels in order to facilitate their entry into constricted openings of soft material rings. This procedure is used to mimic the entry of endoscopes to constricted openings of the human body, like urethra, etc. It is shown that the Re-doped nanoparticles reduce the traction force used to retrieve the metallic lead of the endoscope from the soft ring by a factor close to three times with respect to the original gel. The mechanism of the mitigation of both friction and adhesion forces in these systems by the nanoparticles is discussed.

This minireview outlines the main scientific directions in the research of inorganic nanotubes (INT) and fullerene-like (IF) nanoparticles from layered compounds, in recent years. In particular, this review describes to some detail the progress in the synthesis of new nanotubes, including those from misfit compounds; core-shell and the successful efforts to scale-up the synthesis of WS₂ multiwall nanotubes. The high-temperature catalytic growth of nanotubes, via solar ablation is discussed as well. Furthermore, the doping of the IF-MoS₂ nanoparticles and its influence on the physiochemical properties of the nanoparticles, including their interesting tribological properties are briefly discussed. Finally, the numerous applications of these nanoparticles as superior solid lubricants and for reinforcing variety of polymers are discussed in brief.

Ureteral stents and urethral catheters are commonly used medical devices for maintaining urinary flow. However, long-term placement (>30 days) of these devices in the urinary tracts is limited by the development of encrustation, a phenomenon that holds a prevalence of 50% within this patient population, resulting in a great deal of morbidity to the patients. Here we report the influence of surface coating of an all-silicone catheter with rhenium-doped fullerene-like molybdenum disulfide (Re:IF-MoS₂) nanoparticles on the growth and attachment of in vitro encrustation stones. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) analyses indicated a remarkable attenuation in encrustation occupation on the Re:IF-MoS₂-coated catheter surfaces compared to neat catheters. The doped nanoparticles displayed a unique tendency to self-assemble into mosaic-like arrangements, modifying the surface to be encrustation-repellent. The mechanism of encrustation retardation on the surface coated catheters is discussed in some detail. The ramification of these results for the clogging of other body indwelling devices is briefly discussed. This journal is

The synthesis of inorganic nanotubes (INT) from layered compounds of a small size (

Carbon fullerenes and nanotubes revolutionized understandingof the reactivity of nanoscale compounds. Subsequently, our group and others discovered analogous inorganic compounds with hollow, closed nanostructures. Such inorganic nanostructures offer many applications, particularly in the energy and electronics industries.One way to create inorganic nanostructures is via misfit layer-ed compounds (MLC), which are stacks of alternating two-dimensional molecular slabs, typically held together via weak van der Waals forces. They contain "misfits" in their a-b plane structures that can make them unstable, leading to collapse of the slabs into tubular nanostructures. For example, metal chalcogenide MLCs of the general formula (MX)_1+y/ TX₂ (M = Sn, Pb, Bi, Sb, and other rare earths; T = Sn, Ti, V, Cr, Nb, Ta, etc.; X = S or Se) consist of a superstructure of alternating layers where the MX unit belongs to a (distorted NaCl) orthorhombic symmetry group (O), the TX₂ layer possesses trigonal (T) or octahedral symmetry, and the two layers are held together via both van der Waals and polar forces. A misfit in the a axis or both a and b axes of the two sublattices may lead to the formation of nanostructures as the lattices relax via scrolling. Previous research has also shown that the abundance of atoms with dangling bonds in the rims makes nanoparticles of compounds with layered structure unstable in the planar form, and they tend to fold into hollow closed structures such as nanotubes.This Account shows that combining these two triggers, misfits and dangling bond annihilation in the slab rims, leads to new kinds of nanotubes from MLCs. In particular, we report the structure of two new types of nanotubes from misfits, namely, the SnS/SnS₂ and PbS/NbS₂ series. To decipher the complex structures of these nanotubes, we use a range of methods: high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), selected area electron diffraction (SAED) analyses, scanning electron microscopy (SEM), and Cs-corrected scanning transmission electron microscopy (STEM) in the high-angle annular dark-field mode (HAADF). In both new types, the lattice mismatch between the two alternating sublayers dictates the relative layer-stacking order and leads to a variety of chiral tubular structures. In particular, the incommensuration (a type of misfit) of the SnS₂/SnS system in both the (in plane) a and b directions leads to a variety of relative in-plane orientation and stacking orders along the common c-axis. Thus the SnS/SnS₂ nanotubes form superstructures with the sequence O-T and O-T-T, and mixtures thereof. We also report nanotubes of the misfit layered compound (PbS)_1.14NbS₂, and of NbS ₂ intercalated with Pb atoms, with the chemical formula PbNbS ₂. Thus, the possibility to use two kinds of folding mechanisms jointly offers a new apparatus for the synthesis of unique 1-D nanostructures of great complexity and a potentially large diversity of physicochemical properties.

In this paper the synthesis of inorganic nanotubes (INT) and to a lesser extent, inorganic fullerene-like nanoparticles (IF) of WS₂, which have been recently scaled-up, is discussed in some detail. Subsequently the mechanical properties of IF/INT are summarized, in reference to their remarkable possibility to reinforce polymer matrices and serve as superior solid lubricants. The effect of adding minute amounts of such nanoparticles to various polymer matrices is reviewed with reference to thermoplastic and thermosetting polymers. Possible different applications of such nanocomposites are also briefly discussed.

Recently large amounts of inorganic nanotubes (INT) and inorganic fullerene-like (IF) nanoparticles of WS₂ became available and methods for their dispersion in different media were developed. In the present work the tribological properties of epoxy composite compounded with tungsten disulfide particles of different sizes and morphologies, including quasi-spherical IF nanoparticles, one-dimensional INT as well as micron-size platelets (2H) were investigated. The coefficient of friction and wear loss were measured under dry contact conditions using different tribological rigs. Remarkable reduction in wear and also friction (under high load) was demonstrated for the IF/INT epoxy nanocomposite. The reduced wear is attributed in general to the reinforcement of the polymer matrix by nanoparticles and the simultaneous reduction of the epoxy brittleness. Contrarily, the friction of the neat epoxy sample and epoxy mixed with platelets was accompanied with strong wear and transfer of a polymer film onto the rubbed surfaces. These results are consistent with the recently reported improvements in the fracture toughness, peel and shear strength of the epoxy-nanoparticles (IF/INT) composites.

We report a reasonably high yield (∼50%) synthesis of silicon carbide (SiC) nanowires from silicon oxides and carbon in vacuum, by novel solar and lamp photothermal ablation methods that obviate the need for catalysis, and allow relatively short reaction times (∼10 min) in a nominally one-step process that does not involve toxic reagents. The one-dimensional core/shell β-SiC/SiO_x nanostructures - characterized by SEM, TEM, HRTEM, SAED, XRD and EDS - are typically several microns long, with core and outer diameters of about 10 and 30 nm, respectively. HRTEM revealed additional distinctive nanoscale structures that also shed light on the formation pathways.

We report the first transistor based on inorganic nanotubes exhibiting mobility values of up to 50 cm² V^-1 s^-1 for an individual WS₂ nanotube. The current-carrying capacity of these nanotubes was surprisingly high with respect to other low-dimensional materials, with current density at least 2.4 × 10⁸ A cm^-2. These results demonstrate that inorganic nanotubes are promising building blocks for high-performance electronic applications.

We investigated the infrared vibrational properties of pristine and Re-substituted MoS₂ nanoparticles and analyzed the extracted phonon lifetimes in terms of multiple scattering events. Our measurements reveal both size- and doping-dependent changes that we attribute to grain boundary scattering and charge and mass effects, respectively. By contrast, Born charge is affected only by size. These findings illustrate the utility of reaching beyond traditional bulk semiconductors and quantum dots to explore how doping and confinement impact carrier-phonon interactions in low-dimensional semiconducting nanomaterials.

Mechanical properties and fracture behaviors of multiwalled WS₂ nanotubes produced by large scale fluidized bed method were investigated under uniaxial tension using in situ transmission electron microscopy probing; these were directly correlated to the nanotube atomic structures. The tubes with the average outer diameter ∼40 nm sustained tensile force of ∼2949 nN and revealed fracture strength of ∼11.8 GPa. Surprisingly, these rather thick WS₂ nanotubes could bear much higher loadings than the thin WS ₂ nanotubes with almost "defect-free" structures studied previously. In addition, the fracture strength of the "thick" nanotubes did not show common size dependent degradation when the tube diameters increased from ∼20 to ∼60 nm. HRTEM characterizations and real time observations revealed that the anomalous tensile properties are related to the intershell cross-linking and geometric constraints from the inverted cone-shaped tube cap structures, which resulted in the multishell loading and fracturing.

The tribological properties of rhenium-doped inorganic fullerene-like MoS₂ nanoparticles were studied in poly alpha olefin oil, and compared to inorganic fullerene-like (IF) MS₂ (M=Mo,W) nanoparticles and 2H-MoS₂ platelets. For this purpose a rotational disc tribometer was used. Different regimes in the Stribeck curve, i.e., boundary, mixed and elasto-hydrodynamic lubrication conditions were studied. A precipitous reduction in friction and wear of oil suspensions with nanoparticles were observed for the entire IF samples. However, Re-doped IF exhibited the best results, presumably due to their reduced tribocharging and agglomeration. The various tribological mechanisms of solid state additives are discussed.

A reactivity screening of new nano-hydrodesulfurization (HDS) catalysts was conducted using an ambient pressure flow reactor as well as ultra-high vacuum kinetics techniques. Thiophene was used as a probe molecule. Clean multiwall WS₂ nanotubes (INT-WS₂ ) as well as Ni- and Cocoated INT-WS₂ were considered. In addition, undoped MoS₂ and Re-doped nanoparticles with fullerene-like structures were studied. Commercial Ni and Co HDS catalysts from Haldor Topsoe (Denmark) as well as "nano MoS₂" from Impex Corp. (USA) were considered as reference materials. The lab-synthesized and commercial systems broke down thiophene into quite similar non-sulfur containing products, as identified by a gas chromatograph. The Ni and Co promoted catalysts showed similar thiophene conversion rates. Although the commercial catalysts had larger thiophene conversion rates than the laboratory-synthesized systems, the Re-doped nano-HDS catalyst showed quite low rates of formation of H₂S, an undesirable by-product.

The electrical properties of WS ₂ nanotubes (NTs) were studied through measuring 59 devices. Important electrical parameters, such as the carrier concentration, mobility, and effective barrier height at the contacts, were obtained through fitting experimental non-linear I-V curves using a metal-semiconductor-metal model. The carrier mobility was found to be several orders of magnitude higher than that have been reported previously for WS ₂ NTs. Water absorption was found to decrease the conductivity and carrier mobility of the NTs, and could be removed when the sample was dried. Oxygen absorption also slightly decreased the conductivity of WS ₂ NTs.

WS ₂ nanostructures hold structural characteristics which suggest they will be suitable for heterogeneous catalysis in the hydrodesulfurization (HDS) process. In this work, WS ₂ nanotubes (INT-WS ₂) were coated with cobalt nanoparticles using electroless plating method. Prior to cobalt deposition, the nanotubes surface was activated using palladium seeding process. The deposited cobalt nanoparticles had hcp crystal structure and formed non-uniform layer on the nanotubes surface. The catalytic reactivity of the produced cobalt coated nanotubes toward thiophene decomposition was characterized by an atmospheric flow reactor. The coated nanotubes revealed good catalytic reactivity toward thiophene mineralization. Further, the adsorption kinetics of thiophene on coated INT-WS ₂ was studied by thermal desorption spectroscopy (TDS). The cobalt coated system was found to be more catalytically active than the pristine INT-WS ₂ system. This result is promising since further optimization of the nanofabrication process of the catalyst should increase the conversion rates even further.

A synthetic route for preparation of inorganic WS ₂ nanotube (INT)-colloidal semiconductor quantum dot (QD) hybrid structures is developed, and transient carrier dynamics on these hybrids are studied via transient photoluminescence spectroscopy utilizing several different types of QDs. Measurements reveal efficient resonant energy transfer from the QDs to the INT upon photoexcitation, provided that the QD emission is at a higher energy than the INT direct gap. Charge transfer in the hybrid system, characterized using QDs with band gaps below the INT direct gap, is found to be absent. This is attributed to the presence of an organic barrier layer due to the relatively long-chain organic ligands of the QDs under study. This system, analogous to carbon nanotube-QD hybrids, holds potential for a variety of applications, including photovoltaics, luminescence tagging and optoelectronics. This journal is

Lubricating nanoparticles: The effect of doping semiconductor hollow closed-fullerene-like nanoparticles of MoS ₂ and WS ₂ has been overlooked to date. Rhenium doping of these nanoparticles leads to a marked increase in the nanoparticle's conductivity, reduced agglomeration, and a great reduction in friction and wear (see picture) that approaches superlubricity.

The phenomenon of a partial 2H→1T phase transition within multiwalled WS ₂ nanotubes under substitutional rhenium doping is discovered by means of high-resolution transmission electron microscopy. Using density-functional tight-binding calculations for the related MoS ₂ compound, we consider a possible origin of this phase transition, which was known formerly only for WS ₂ and MoS ₂ intercalated by alkali metals. An interplay between the stability of layered or nanotubular forms of 2H and 1T allotropes is found to be intimately related with their electronic structures and electro-donating ability of an impurity.

It is now possible to synthesize inorganic nanotubes (INT) of WS2 in a pure phase and substantial amounts. Due to their crystalline perfection, they are characterized by excellent mechanical behavior. This study is dedicated to the investigation of the effect of INT-WS2 on the mechanical, thermal, adhesion and tribological properties of epoxy based nanocomposites. Various concentrations up to 1.0 wt% of the INT were added to the epoxy matrix. First a method was developed to mix the nanotubes in the epoxy resin matrix. A combination of both magnetic stirring and ultrasonic mixing was used. The adhesion, fracture toughness and strain energy release rate were studied. The INT-WS2 were found to significantly improve all these properties. The wear of the nanotubes-reinforced epoxy was eight-times lower than that of pure epoxy. These results suggest numerous applications.

In this work chromium-rich coatings impregnated with fullerene-like (IF)-WS₂ nanoparticles were deposited on stainless steel substrates. The coatings were obtained from a trivalent chromium bath at pH 2 by galvanostatic electrodeposition. Zinc and cobalt salts were added to the aqueous solution in small amounts serving as cationic growth promoters. Photodeposition of tin-palladium nanoparticles was used as seeding enhancer for the co-deposition of the fullerene-like nanoparticles. The coatings were characterized by a number of techniques and were found to show a decreasing gradient of the IF nanoparticles towards the film-substrate interface. Tribological tests showed that in contrast to the substrate and the pure metal coating, the IF-containing films exhibit low friction and wear.

We report on the synthesis of inorganic fullerene-like molybdenum disulfide (MoS₂) nanoparticles by pulsed laser ablation (PLA) in water. The final products were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and resonance Raman spectroscopy, etc. Cell viability studies show that the as-prepared MoS₂ nanoparticles have good solubility and biocompatibility, which may show a great potential in various biomedical applications. It is shown that the technique of PLA in water also provides a green and convenient method to synthesize novel nanomaterials, especially for biocompatible nanomaterials.

The ability to form blends of polymers offers the opportunity of creating a new class of materials with enhanced properties. In addition to the polymer components, recent advances in nanoengineering have resulted in the development of nanosized inorganic particles that can be used to improve the properties of the blend, such as the flammability and the mechanical properties. While traditional methods using copolymer compatibilizers have been used to strengthen polymer blends, here, we show that the inorganic nanosized filler additive can also serve as a compatibilizer as it can localize to the interface between the polymers. We use experimental and theoretical studies to show the fundamental mechanisms by which inorganic fillers with large aspect ratio and at least one-dimension in the nanometer range, can act as non-specific compatibilizers for polymer blends. We examine a series of nanosized fillers, ranging from nanotubes to nanoclays (with varying aspect ratios) in a model polystyrene (PS)/poly(methylmethacyralate) (PMMA) blend. Using a number of experimental techniques such as transmission electron microscopy (TEM), scanning tunneling X-ray microscopy (STXM), and atomic force microscopy (AFM) we postulate that the mechanism of compatibilization occurs as a result of the fillers forming in situ grafts with the immiscible polymers. We also use theoretical studies to show that the aspect ratio and the bending energy of the fillers play a key role in the compatibilization process. Our results indicate that the compatibilization is a general phenomenon, which should occur with all large aspect ratio nanofiller additives to polymer blends.

A track record of generating novel fullerene-like and nanotubular inorganic nanostructures from Cs₂O, SiO_2-x, WS₂, and MoS₂ by photothermal ablation with highly concentrated sunlight and ultra-bright lamp light is reviewed, and augmented with new results for exfoliated MoS₂ and carbon as well as carbon nanotubes.

Inorganic layered materials can form hollow multilayered polyhedral nanoparticles. The size of these multi-wall quasi-spherical structures varies from 4 to 300 nm. These materials exhibit excellent tribological and wear-resisting properties. Measuring and evaluating the stiffness of individual nanoparticle is a non-trivial problem. The current paper presents an in situ technique for stiffness measurements of individual WS₂ nanoparticles which are 80 nm or larger using a high resolution scanning electron microscope (HRSEM). Conducting the experiments in the HRSEM allows elucidation of the compression failure strength and the elastic behavior of such nanoparticles under uniaxial compression.

New materials and techniques pertaining to the synthesis of inorganic nanotubes have been ever increasing since the initiation of the field in 1992. Recently, WS2 nanotubes, which are produced now in large amounts, were filled with molten lead iodide salt by a capillary wetting process, resulting in PbI₂@WS₂ core-shell nanotubes. This work features progress in the synthesis of new core-shell nanotubes, including Bil₃@WS ₂ nanotubes produced in a similar same manner. In addition, two new techniques for obtaining core-shell nanotubes are presented. The first is via electron-beam irradiation, i.e., in situ synthesis within a transmission electron microscope. This synthesis results in SbI₃ nanotubes, observed either in a hollow core Of WS₂ ones (Sbl₃@WS ₂ nanotubes), or atop of them (WS₂@Sbl₃ nanotubes). The second technique involves a gaseous phase reaction, where the layered product employs WS₂ nanotubes as nucleation sites. In this case, the MoS₂ layers most often cover the WS₂ nanotube, resulting in WS₂@MoS₂ core-shell nanotubes. Notably, superstructures of the form MoS₂@WS₂ are occasionally obtained. Using a semi-empirical model, it is shown that the Pbl₂ nanotubes become stable within the core of MoS2 nanotubes only above a critical core diameter of the host (>12 nm); below this diameter the PbI₂ crystallizes as nanowires. These model calculations are in agreement with the current experimental observations, providing further support to the growth mechanism of such core-shell nanotubes.

In this work the effect of inorganic fullerene-like (closed cages) nanoparticles of tungsten disulfide (IF-WS₂) on the mechanical properties and especially on the toughness of epoxy resins, was studied. The epoxy resin used was the well-known DGEBA (di-glycidyl ether of bis-phenol A) cured with polyamidoamine. The epoxy/IF-WS₂ nanocomposites were prepared by applying a high shear mixing to obtain a uniform dispersion and homogeneous distribution of the IF nanoparticles in the epoxy matrix. Two mixing procedures were used - a low shear of short duration and high shear with a long mixing time. The resulting epoxy nanocomposites were first characterized for their shear and peel strength using appropriate bonded joints. The experimental results demonstrate that enhanced shear strengths and shear moduli were achieved, together with a significant increase in the peel strengths at low concentrations of the IF-WS₂ nanoparticles (more than 100% increase at 0.5 wt% IF-WS₂). Above the threshold value of 0.5% IF-WS ₂ the peel strength decreased sharply. The fractured surfaces of the bonded joints were examined by transmission and scanning electron microscopy in order to characterize the fracture mechanisms and analyze the dispersion level of the nanoparticles within the polymer. The electron micrographs indicated that the presence of the nanoparticles in the epoxy matrix induced fracture mechanisms which were different from those observed in the pristine epoxy phase. These mechanisms included: crack deflection; crack bowing; and crack pinning. Evidence for a chemical interaction between the nanoparticles and the epoxy were obtained by infrared measurements in the attenuated total transmittance mode. The data suggests the formation of new carbon-oxygen-sulfur bonds, which are most likely due to the reaction of the outermost sulfur layer of the IF nanoparticles with the reactive epoxy groups. The observed simultaneous increase in both shear and peel strengths at very low IF-WS₂ concentrations, found in this work, could lead to the development of high performance adhesives and to new types of structural and ballistic fiber nanocomposites.

WS₂ nanotubes have been filled and intercalated by molten phase caesium iodide. The presence of caesium iodide inside the WS₂ nanotubes has been determined using high-resolution transmission electron microscopy (HRTEM) coupled with electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDS). Noticeably, a Moiré pattern was observed due to the interference between encapsulated CsI and WS₂ layers. The intercalation of CsI into the host concentric WS₂ lattices resulted in an increase in the interplanar spacing.

Numerous examples of closed-cage nanostructures, such as nested fullerene-like nanoparticles and nanotubes, formed by the folding of materials with layered structure are known. These compounds include WS₂, NiCl₂, CdCl₂, Cs₂O, and recently V₂O₅. Layered materials, whose chemical bonds are highly ionic in character, possess relatively stiff layers, which cannot be evenly folded. Thus, stress-relief generally results in faceted nanostructures seamed by edge-defects. V₂O₅, is a metal oxide compound with a layered structure. The study of the seams in nearly perfect inorganic "fullerene-like" hollow V₂O₅ nanoparticles (NIFV₂O₅) synthesized by pulsed laser ablation (PLA), is discussed in the present work. The relation between the formation mechanism and the seams between facets is examined. The formation mechanism of the NIF-V₂O₅ is discussed in comparison to fullerene-like structures of other layered materials, like IF structures of MoS₂, CdCl₂, and Cs₂O. The criteria for the perfect seaming of such hollow closed structures are highlighted.

Using a new quartz-made reactor, large amounts of fullerene-like (IF) MoS ₂ nanoparticles were synthesized by reacting MoO ₃ vapor with H ₂S in a reducing atmosphere. The nanoparticles were found to be of high crystalline order; with an average size of 70 nm and consist of more than 30 closed shells. Extensive tribological testing of the nanoparticles in two types of synthetic oils- poly-alpha olefins (PAO)- was carried out and compared to that of bulk (2H platelets) MoS ₂ and IF-WS ₂. These tests indicated that under high pressure and relatively low humidity, the IF-MoS ₂ exhibited a friction coefficient as low as 0.03 and the smallest wear rate of the measured systems. However, its performance was found to be lower in comparison to IF-WS ₂ after 2500 cycles, due probably to its inferior chemical stability. This study indicates that the tribological performance of the IF nanoparticles depends strongly on their crystalline order and size.

Inorganic fullerene-like WS₂ and MoS₂ nanoparticles have been synthesized using exclusively solid precursors, by reaction of the corresponding metal oxide nanopowder, sulfur and a hydrogen-releasing agent (NaBH₄ or LiAlH₄), achieved either by conventional furnace heating up to a 900 °C or by photothermal ablation at far higher temperatures driven by highly concentrated white light. In contrast to the established syntheses that require toxic and hazardous gases, working solely with solid precursors permits relatively safer reactor conditions conducive to industrial scale-up.

With the emergence and commercialization of nanoparticles, new opportunities have emerged for toughening of epoxy adhesives using nanoparticles without sacrificing strength, rigidity and glass transition temperature, as is the case with conventional elastomeric tougheners. Inorganic Fullerene-like tungsten disulfide (IF-WS₂) nanoparticles and functionalized nano-POSS (Polyhedral-Oligomeric-Sil-Sesquioxane) were used to study the effects of nanoparticles on the toughening and mechanical properties of low and high temperature curing epoxy systems. Experimental results indicated that IF-WS ₂ increased the fracture toughness by more than 10 fold in both epoxy systems at very low concentrations (0.3-0.5 wt%) while increasing its storage modulus and preserving its glass transition temperature. Epoxy functionalized POSS demonstrated an increase in toughness in addition to preserving rigidity and thermal properties at higher concentrations (3 wt%). It was postulated that chemical interaction of the sulfide and the epoxy matrix and the inherent properties of WS₂ were the decisive factors with respect to the outstanding nano-effect in the case IF-WS₂.

Further understanding of the growth mechanism and the detailed structure of fullerene-like MoS₂ (IF-MoS₂) nanoparticles was achieved by using a new kind of reactor. The annealed nanoparticles consist of >30 closed layers and their average diameter is 50-80 nm although a small (

The synthesis of WS2 inorganic nanotubes (INT) and inorganic fullerene-like (IF) structures in 1992 signified the opening of a fertile and challenging field of scientific endeavor. These structures were the first of a long and ever-expanding series of INT and IF structures. Although initially much of the effort concentrated on the synthesis of INT and IF from compounds with layered structures, recently there his been a surge of efforts to synthesize crystalline and polycrystalline nanotubular structures from compounds with quasi-isotropic structures, like spinels, BaTiO3, SiO2, TiO2, and many others. The present review summarizes some of the progress in this field in recent years. Much of the progress in this field was achieved through strong interaction between theoretical and experimental work. This article has four themes: (a) new synthetic approaches leading to new kinds of Wand INT; (b) study of the molecular structure Of Such nanoparticles with new tools, such as aberration-corrected transmission electron microscopy (TEM) and high-angle annular dark field (HAADF); (c) recent progress in the investigation of the properties of such nanostructures; and (d) examples of applications for which clear progress has been accomplished, in particular in solid lubrication and high-strength nanocomposites.

We experimentally observed atomic-scale torsional stick-slip behavior in individual nanotubes of tungsten disulfide (WS₂). When an external torque is applied to a WS₂ nanotube, all its walls initially stick and twist together, until a critical torsion angle, at which the outer wall slips and twists around the inner walls, further undergoing a series of stick-slip torque oscillations. We present a theoretical model based on density-functional-based tight-binding calculations, which explains the torsional stick-slip behavior in terms of a competition between the effects of the in-plane shear stiffness of the WS₂ walls and the interwall friction arising from the atomic corrugation of the interaction between adjacent WS₂ walls.

The characterization of nanostructures down to the atomic scale is essential to understand some physical properties. Such a characterization is possible today using direct imaging methods such as aberration-corrected high-resolution transmission electron microscopy (HRTEM), when iteratively backed by advanced modeling produced by theoretical structure calculations and image calculations. Aberration-corrected HRTEM is therefore extremely useful for investigating low-dimensional structures, such as inorganic fullerene-like particles and inorganic nanotubes. The atomic arrangement in these nanostructures can lead to new insights into the growth mechanism or physical properties, where imminent commercial applications are unfolding. This article will focus on two structures that are symmetric and reproducible. The first structure that will be dealt with is the smallest stable symmetric closed-cage structure in the inorganic system, a MoS₂ nanooctahedron. It is investigated by means of aberration-corrected microscopy which allowed validating the suggested DFTB-MD model. It will be shown that structures diverging from the energetically most stable structures are present in the laser ablated soot and that the alignment of the different shells is parallel, unlike the bulk material where the alignment is antiparallel. These findings correspond well with the high-energy synthetic route and they provide more insight into the growth mechanism. The second structure studied is WS ₂ nanotubes, which have already been shown to have a unique structure with very desirable mechanical properties. The joint HRTEM study combined with modeling reveals new information regarding the chirality of the different shells and provides a better understanding of their growth mechanism.

The time dependent chemical changes occurring at the surface of inorganic fullerene-like (IF) nanoparticles of WS₂ were investigated using X-ray photoelectron spectroscopy (XPS) and compared to those of bulk powder, 2H-WS₂. It was possible to follow the long term surface oxidation and carbonization occurring at defects on the outermost surface (0001) molecular layers of the inorganic fullerene-like nanoparticles. Vacuum annealing was shown to remove most of these contaminants and bring the surface close to its pristine stoichiometric composition. In accordance with previous measurements, further evidence was obtained for the existence of water molecules, which were entrapped in the hollow core and interstitial defects of the fullerene-like nanoparticles during the synthesis. These water molecules were also shown to be removable by the vacuum annealing process. Chemically resolved electrical measurements (CREM) in the XPS showed that the IF samples had become less p-type after the vacuum annealing. Finally, tribological measurements showed that the vacuum annealed IF samples performed better as an oil additive than the non-annealed IF samples and the 2H-WS₂ powder.

WS₂ inorganic fullerene-like (IF) nanoparticles were subjected to intercalation with potassium, sodium, and rubidium atoms in heated sealed ampules. The product of the intercalation process was not pure and was composed of both intercalated and nonintercalated phases. X-ray diffraction measurements under inert conditions of the intercalated powders showed that the interlayer expansion was correlated with the alkali metal radius. Small increase of the a-axis was observed as well and was explained on the grounds of the WS₂ band structure. The XPS analysis of the rubidium intercalated material showed a rise in the Fermi energy as a result of the intercalation, endowing the originally p-type nanoparticles an n-type character.

Inorganic fullerene-like (IF) nanoparticles and nanotubes of WS₂ were synthesized by a gas phase reaction starting from WCl_n (n = 4, 5, 6) and H₂S. The effect of the various metal chloride precursors on the formation of the products was investigated during the course of the study. Various parameters have been studied to understand the growth and formation of the IF-WS₂ nanoparticles and nanotubes. The parameters that have been studied include flow rates of the various carrier gases, heating of the precursor metal chlorides and the temperature at which the reactions were carried out. The best set of conditions wherein maximum yields of the high quality pure-phase IF-WS₂ nanoparticles and nanotubes are obtained have been identified. A detailed growth mechanism has been outlined to understand the course of formation of the various products of WS₂.

This review summarizes recent work on the polymer-assisted fabrication of well-defined inorganic and organic nanoparticles with controlled shape, size, and functional properties. The discussion concentrates on the physical-chemical aspects of the problem. Special attention is paid to the preparation of nanocomposites with individual (non-aggregated) nanoparticles with narrow size distribution and versatile morphologies, including the design of nanoparticles and nanocomposites that can serve multifunctional purposes. We have focused also on the problem of the spatial arrangement of nanoparticles and elucidation of the role of polymers in this process because it is a key problem in nanotechnology industrialization. The potential applications of nanoparticles encapsulated in polymers and in nanocomposites are briefly discussed. We try also to emphasize the synergistic role of the ingredients on the performance of nanocomposites.

Solar ablation creates the sharp radiative and temperature gradients, as well as the high-temperature annealing environment, that favor nanomaterial syntheses. Using highly concentrated sunlight, we generated fullerene-like MoS₂, ranging from single-walled nanotubes and closed-cage structures to their larger multi-walled counterparts. TEM, HRTEM and EDS unambiguously established the nanostructures, some achieving fundamentally minimum sizes predicted by molecular structural theory. Irradiation of MoS₂ and powdered mixtures of MoS₂ + SiO₂ in evacuated quartz ampoules also generated nanofibers and nanospheres of amorphous SiO₂: the first production of SiO₂ nanostructures purely from quartz. Also, solar ablation of MoS₂ + SiO mixtures produced nanowires and nanospheres of crystalline Si.

It is already well established today that numerous materials form closed-cage structures, of which carbon fullerenes and nanotubes are a special case [1]. Inorganic fullerene-like nanoparticles (designated IF) and inorganic nanotubes (INT) have been produced by different routes and experimental techniques, achieving persistent growth of a variety of materials and structural wealth within them. The research in this area has focused on synthesizing new IF and INT materials and understanding their different properties as well as scaling up the synthetic process in order to make it suitable for industrial applications. In this review, the main synthetic procedures to obtain inorganic fullerene-like nanoparticles and nanotubes will be discussed alongside with the different mechanisms that affect the morphology of the final product. The main differences between the morphologies will be presented. Some general considerations relating the properties of the parent compound with the morphology of the product will be mentioned.

Their mesoscopic dimensions (including a nanometer scale diameter and a micrometer scale length) make nanotubes a unique and attractive object of study, including the study of their mechanical properties and fracture in particular. The investigation of the mechanical properties of individual WS2 nanotubes is a challenging task due to their small size. Hence, various microscopy based techniques were used to overcome this challenge. The Young's modulus was studied by techniques like atomic force microscope (AFM) and scanning electron microscope (SEM); it was also calculated by using the density-functional-based tight-binding (DFTB) method. Tensile tests and bending tests of individual WS2 nanotubes were performed as well. Furthermore, the shock wave resistance of these nanotubes was tested. The Young's modulus of WS2 nanotubes was found to be in the range of 150-170 GPa, which is in good agreement with DFTB calculations. WS2 nanotubes also showed tensile strength as high as 16 GPa and fracture strain of 14%. These results indicate the high quality of these nanotubes which reach their theoretical strength. The interlayer shear (sliding) modulus was found to be ca. 2 GPa, this value is in good agreement with DFTB calculations. Moreover, the nanotubes were able to withstand shock waves as high as 21 GPa.

The cylindrical geometry of nanotubes dictates a strong anisotropy of their physical properties. In practice, the difficulty in extracting individual components of the elastic tensor has limited the available information to only very partial and indirect experimental data. Here, the interlayer shear (sliding) modulus (C₄₄) of single multiwalled WS₂ nanotubes was studied by atomic force microscopy bending tests. The observed value of 2 GPa agrees well with the value of 4 GPa obtained for density functional tight binding calculations for 2H-MoS₂. This value of the shear modulus represents a much higher degree of anisotropy than that obtained for carbon nanotubes and enables assignment of the mode of shear deformation.

Inorganic fullerene-like (IF) solid lubricant nanoparticles and nanotubes with extremely useful mechanical and tribological characteristics have been realized, offering a plethora of new applications for these nanomaterials. The IF nanoparticles were found to be in the aggregated state. It is expected that the size of the aggregates and their distribution determine the penetration and entrapping of IF nanopowder into the interface. The main goal of the present work is to elucidate the effect of the mixing time of IF-WS₂ nanomaterial in the oil on the size of the IF aggregates and their influence on the friction and wear. The fraction of small aggregates increases and that of the large aggregates decreases with longer mixing time. Consequently, the spread of the tribological results diminishes with the lengthening of the mixing time. The reproducibility of the friction results for the pairs lubricated with oil +IF nanoparticles is determined by distribution of the IF aggregates in the lubricant and the size of the solid lubricant aggregates.

MoS₂ nanooctahedra are believed to be the smallest stable closed-cage structures of MoS₂, i.e., the genuine inorganic fullerenes. Here a combination of experiments and density functional tight binding calculations with molecular dynamics annealing are used to elucidate the structures and electronic properties of octahedral MoS₂ fullerenes. Through the use of these calculations MoS₂ octahedra were found to be stable beyond n_MO > 100 but with the loss of 12 sulfur atoms in the six corners. In contrast to bulk and nanotubular MoS₂, which are semiconductors, the Fermi level of the nanooctahedra is situated within the band, thus making them metallic-like. A model is used for extending the calculations to much larger sizes. These model calculations show that, in agreement with experiment, the multiwall nanooctahedra are stable over a limited size range of 10⁴-10⁵ atoms, whereupon they are converted into multiwall MoS₂ nanoparticles with a quasi-spherical shape. On the experimental side, targets of MoS₂ and MoSe₂ were laser-ablated and analyzed mostly through transmission electron microscopy. This analysis shows that, in qualitative agreement with the theoretical analysis, multilayer nanooctahedra of MoS₂ with 1000-25 000 atoms (Mo + S) are stable. Furthermore, this and previous work show that beyond ∼10⁵ atoms fullerene-like structures with quasi-spherical forms and 30-100 layers become stable. Laser-ablated WS₂ samples yielded much less faceted and sometimes spherically symmetric nanocages.

A simple, inexpensive, and reproducible photothermal procedure for synthesizing IF-Cs₂O nanoparticles with immensely concentrated sunlight was demonstrated. The solar-driven synthesis of IF-Cs₂O was performed in evacuated quartz ampoules that contained 3R-Cs₂-O crystallites under continuous irradiation with a concentrated solar power of 2.0-7.7 W, and periods ranging from 30 to 840 s. Samples were collected from the deposit that gathered on the quartz ampoule during the solar irradiation for TEM analysis. The interaction of the beam with the materials led to thermal motion, charging, desorption of trace quantities, or possible chemical changes. The results of the electron energy loss spectroscopy and imaging with a Gatan imaging filters proved that only cesium and oxygen were present in the nanoparticles.

We have proposed in 1992 that nanoparticles of layered compounds will be unstable against folding and close into fullerene-like structures and nanotubes (IF). Nanotubes and fullerene-like structures were prepared from numerous compounds with layered and recently also non-layered structure by various groups. Much progress has been achieved in the synthesis of inorganic nanotubes and fullerene-like nanoparticles of WS₂ and MoS₂ and many other metal dichalcogenides over the last few years. Substantial progress has been accomplished in the use of such nanoparticles for tribological applications and lately for impact resilient nanocomposites. These tests indicated that IF-MoS₂ and IF-WS₂ are heading for large scale applications in the automotive, machining, aerospace, electronics, defense, medical and numerous other kinds of industries. A few products based on these nanoparticles have been recently commercialized by "ApNano Materials, Inc". Novel applications of inorganic nanotubes and fullerene-like nanoparticles in the fields of catalysis; microelectronics; Li rechargeable batteries; medical and opto-electronics will be discussed.

Inorganic fullerene-like nanoparticles of WS ₂ (IF-WS ₂), are synthesized by a reaction of tungsten oxide with molecular hydrogen and hydrogen sulfide. The synthesized nanoparticles appear as large agglomerates (>40 microns), each one counting thousands of IF nanoparticles. ¹H nuclear magnetic resonance study of these nanoparticles is reported. The measurements show that the prepared product contains water (and possibly some hydrogen) molecules that occupy the voids in the central part of the fullerene-like nanoparticles and the nanopores between the adhering IF-WS ₂ particles. Defects in the IF-WS ₂ structure, arising due to the strain release during the folding of the layers, may result in additional sites for the absorbed water. Vacuum annealing of the powder leads to substantial reduction in the amount of absorbed water molecules.

Current-voltage characteristics measured using STM on fullerene-like WS₂ nanoparticles show zero-bias current and contain segments in which the tunneling current flows opposite to the applied bias voltage. In addition, negative differential conductance peaks emerge in these reversed current segments, and the characteristics are hysteretic with respect to the change in the voltage sweep direction. Such unusual features resemble those appearing in cyclic voltammograms, but are uniquely observed here in tunneling spectra measured in vacuum, as well as in ambient and dry atmosphere conditions. This behavior is attributed to tunneling-driven electrochemical processes.

Fullerene-like WS₂ (MoS₂) nanoparticles (IF) have been studied in the past. Their efficacy as additives for lubrication fluids has been demonstrated. It was shown that the IF nanoparticles are usually delaminated in the inlet of the smooth contact. Thin sheets of broken IF nanoparticles can be entrapped between the rubbed surfaces and thus favorably affect the friction and the wear. Friction pairs at real mechanical macrosystems are often subjected to friction-induced vibrations. It was shown that the mechanical excitations can improve the supplying and preservation of fluid lubricant film in the interface. It can be hypothesized that under vibrations in a definite range of frequencies and amplitudes, the probability for small IF aggregates to be entrapped into the interface is increased. The main goal of this work was to study the effect of artificial mechanical excitations on the friction and wear of contact pairs rubbed with nanoparticles. In order to avoid friction-induced excitations, a new ball-on-flat friction device was developed. The frequency and the amplitude of the ball were varied using a motion of miniature micromotor attached to the ball holder. The behavior of IF nanoparticles in friction tests with and without external mechanical excitations was compared with the tribological behavior of the contact pair lubricated with pure paraffin oil. It was found that the external mechanical excitation of the mechanical parts rubbed with nanoparticles allows a penetration of these nanoparticles into interface. This effect leads to a remarkable shortening of the run-in period and improves the tribological properties of contact pairs. From the present results it may be anticipated that the accidental friction-induced vibrations, which are determined by the stiffness and damping force of the device, lead to preferential penetration of the IF nanoparticles into the contact area, affecting thereby the tribological behavior of the interface.

Although graphite, with its anisotropic two-dimensional lattice, is the stable form of carbon under ambient conditions, on nanometre length scales it forms zero- and one-dimensional structures, namely fullerenes and nanotubes, respectively. This virtue is not limited to carbon and, in recent years, fullerene-like structures and nanotubes have been made from numerous compounds with layered two-dimensional structures. Furthermore, crystalline and polycrystalline nanotubes of pure elements and compounds with quasi-isotropic (three-dimensional) unit cells have also been synthesized, usually by making use of solid templates. These findings open up vast opportunities for the synthesis and study of new kinds of nanostructures with properties that may differ significantly from the corresponding bulk materials. Various potential applications have been proposed for the inorganic nanotubes and the fullerene-like phases. Fullerene-like nanoparticles have been shown to exhibit excellent solid lubrication behaviour, suggesting many applications in, for example, the automotive and aerospace industries, home appliances, and recently for medical technology. Various other potential applications, in catalysis, rechargeable batteries, drug delivery, solar cells and electronics have also been proposed.

We measured the infrared vibrational properties of bulk and nanoparticle W S2 in order to investigate the structure-property relations in these materials. In addition to the symmetry-breaking effects of local strain, nanoparticle curvature modifies the local charging environment of the bulk material. Performing a charge analysis on the xy -polarized E1u vibrational mode, we find an approximate 1.5:1 intralayer charge difference between the layered 2H material and inorganic fullerene-like (IF) nanoparticles. This effective charge difference may impact the solid-state lubrication properties of nanoscale metal dichalcogenides.

TiS2 nanoparticles with nested fullerene-like structure (IF) 60-120 nm in size consisting of up to 100 concentric molecular layers and having quite a perfectly spherical shape were obtained by reacting TiCl4 and H2S using first a horizontal and subsequently a vertical reactor. The proposed growth mechanism of these nanoparticles, i.e. nucleation and growth, is radically different from the one proposed for the growth of the fullerene-like WS2 from the respective oxide nanoparticles. It was found that adding 1-2% IF-TiS2 improves the behavior of lubricating oil substantially. The improved performance of the additive was attributed to the nearly spherical shape of the nanoparticles which promotes rolling friction.

We obtained a Raman signal from an individual WS2 nanotube mounted on an atomic force microscopy cantilever tip. We discuss the implications for simultaneous investigations of the mechanical properties of WS2 nanotubes by combining different experimental methods. From the orientation dependence of this nanotube's resonant Raman intensity, we estimate the ratio of the perpendicular to parallel polarizabilities αXX\u2022αZZ\u20300.16. We compare the WS2 nanotube with single-walled carbon nanotubes and expect a similarly strong depolarization effect for multiwalled carbon nanotubes.

We present the results from an experimental study of the magnetotransport of superconducting wires of amorphous indium-oxide having widths in the range 40-120 nm. We find that, below the superconducting transition temperature, the wires exhibit clear, reproducible, oscillations in their resistance as a function of magnetic field. The oscillations are reminiscent of those that underlie the operation of a superconducting quantum interference device.

(Figure Presented) Fullerene-like Cs₂O nanoparticles were prepared by laser ablation of 3R-Cs₂O powder in evacuated quartz ampoules. The Cs₂O closed cages, such as the faceted nanoparticle shown in the picture, are remarkably stable as compared with the corresponding extremely unstable but technically important bulk compound, which makes them potentially useful in applications involving cesium oxide coatings, for example, photoemissive devices and catalytic converters.

The dynamic pressure-resitance capacity of inorganic fullerene (IF) cages in uniaxial shockwave pressures up to 30 GPa, was studied. It was observed that to a limit of 25 GPa, except those IFs mixed with nanotubes, others suffered light damages. It was also observed that a perfectly hollow and small IF cage consists an ability to withstand much higher shock wave pressure. These inorganic fullerenes can be used as lubricant at severe loading conditions, or as a coating or composite phase in cases of anti-shock or high-pressure environment.

Nanoparticles of WS₂ and MoS₂ with a closed cage structure (fullerene-like) that are termed IF phases are synthesized in large amounts in a pure form. These nanoparticles were shown to play a favorable role as solid lubricants under severe conditions where fluids are unable to support the heavy load and are squeezed away from the contact area. Various tribological scenarios are presented for these superior solid lubricants, demonstrating the large scale potential for applications of these materials. The mechanism of action of these solid lubricants is briefly discussed. Various other potential applications of IF phases for nanocomposites with high impact resistance; in rechargeable batteries and in optical devices are discussed in short.

When dispersed in a synthetic polyalphaolefin (PAO) base oil, inorganic fullerene-like (IF-MS₂) nanoparticles of metal dichalcogenides (IF-MoS₂, IF-WS₂, IF-NbS₂) lead to a significant reduction of both friction and wear under boundary lubrication. The effect of the contact pressure on the tribological properties of IF nanoparticles is particularly interesting. Results show that the higher is the pressure, the lower is the friction coefficient. The effect of the concentration shows that, even used at a low concentration (0.1%wt), IF-MS₂ is able to decrease friction (0.05) compared to base oil only (0.08). A steady state friction coefficient of 0.04 was reached with IF-WS₂ at 1%wt in PAO. Friction-induced transformation of the IF-MS₂ nanoparticles into H-MS₂ single sheets was evidenced by High Resolution Transmission Electron Microscopy (HRTEM). Some of these superimposed sheets are found in incommensurate positions, thus possibly explaining the very low friction coefficient of 0.04 obtained with IF-WS₂. In-situ Raman spectroscopy was performed during a friction test to follow this structural modification. The lubrication mechanism of IF-MS₂ is very similar to a "drug delivery system". A very low concentration of additives is sufficient and the activation is obtained by the opening of the nested structure, like in certain micellar structures. Furthermore, no chemical reaction is required to obtain interesting properties. Thus, fullerene-like nanoparticles are active at the very beginning of the test and even at ambient and low temperature.

Adding guest atoms to inorganic nanotubes, known as 'doping', influences their room-temperature magnetic properties - properties that could be exploited in 'spintronic' devices and computer memory.

Cesium oxides are materials of great interest to the photodetection industry because of their relatively low work function (∼1 eV). Used mainly as coating films for photoemissive devices, they provide high wavelength thresholds and high photocurrents. However, they are unstable, air-sensitive, and hygroscopic, rendering them short-lived and limiting their applications. Although the technology of these devices is highly developed, their characterization on the micro- and nanoscale suffers from their poor chemical stability and poor crystallinity. In the present study, cesium oxides were synthesized from the elements and were characterized using a combination of chemical and structural analysis techniques. Because the reaction products were extremely sensitive to humidity, sample analysis without atmospheric exposure was essential, and techniques were developed for the transfer of the samples to the measurements systems. Extensive data obtained from X-ray energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD), and Raman microscopy were obtained. Raman spectra with bands at 103, 742, and 1134 cm^-1 strongly confirmed the presence of the oxide, peroxide, and Superoxide ions, respectively, as well as the absence of carbonate as an impurity. The A_1g mode of Cs₂O was detected as an anti-Stokes band at 103 cm^-1. This study provides further insight into the reactivity of the various cesium oxides.

Inorganic fullerene-like materials have been identified as being of potentially utmost importance for many industrial applications. MoS₂ and WS₂ hollow nanoparticles have been identified as strong candidates for tribological applications such as solid lubricants. The main goal of this work was to evaluate the mechanical properties of solid lubricant particles in ensemble under hydrostatic pressure. The behavior of nanopowders under compression has been described on the basis of constitutive models of continuum mechanics. The model will be applied to an isotropic compaction of copper (well-studied medium), fullerene-like (IF-WS₂) nanoparticles and a natural powder of 2H-WS₂ platelets. The morphology of individual nanoparticles and nanoparticle ensembles will be examined and discussed. Another aspect of this work was to study the applicability and limitations of the proposed constitutive model for the understanding of the tribological behavior of solid lubricant nanoparticles. Compression with the maximal pressure (500 MPa) showed that the shape of the IF nanoparticles is preserved. The dominant mechanism of damage was found to be the delamination or peeling-off of the external sheets of hollow nanoparticles. Strong destruction of 2H-WS₂ platelets was observed under compression.

Pronounced surface diffusion is observed during x-ray photoelectron spectroscopy measurements of 2H platelets and inorganic fullerene-like (IF) MS2 (M=WMo) powders, intercalated with alkaline (A=K,Na) elements. Using controlled surface charging the intercalants migrate towards the surface, where they oxidize. This dry deintercalation is controllable via external charging parameters, yet showing that internal chemical and structural parameters play an important role in the process. Diffusion rates out of 214 matrixes are generally higher than in corresponding IF samples. Clear differences are also found between Mo and W-based systems. Application of this approach into surface modification and processing is, proposed. (C) 2003 American Vacuum Society.

It was shown previously that nanoparticles of layered comppunds form closed-cage and nanotubular structures. These nanostructures received the generic name of inorganic fullerene-like (IF) materials. In particular nanoparticles of metal dihalides, like NiCl₂ and CdCl₂, were shown to form such closed-cage structures in the past. In the present report faceted IF-CdI₂ nanoparticles encapsulating a Cd core are reported. These nanoparticles were obtained using electron beam irradiation of the source powder of CdI₂. The faceted nanoparticles exhibit one of two morphologies: hexagonal or elongated rectangular characters. The nanoparticles can be considered as core (Cd)-shell (CdI₂) nanostructures. Consistent with previous observations, this study shows that the seamless structure of the IF materials can stabilize phases, which are otherwise unstable Under the electron-beam irradiation. The growth mechanism of these nanostructures is briefly discussed.

WS₂ nanoparticles with closed-cage structure (fullerene-like IF) are already being synthesized in macroscopic amounts from the respective oxide nanoparticles. They have been studied as superior solid lubricants under harsh conditions in recent years. Under severe contact conditions both fluids and greases are squeezed out from the contact area and consequently do not provide adequate lubrication conditions. Addition of even a small amount of IF nanoparticles to the oil was found to reduce the friction coefficient and wear rate, and increase the load-bearing capacity of the friction pairs. Furthermore, IF nanoparticles were impregnated into polymer and metal coatings and into self-lubricating porous metal parts, and were found to alleviate both friction and wear remarkably well. In another set of experiments, IF nanoparticles were shown to provide excellent tribological behavior for the contact between a ceramic alumina block and silicon nitride ball. The mechanism for the improved tribological behavior of the IF nanoparticles is being investigated. In addition to the rolling friction, gradual exfoliation of the IF onions and transfer of monomolecular WS₂ sheets onto the metal surface (third body transfer) is shown to play a major role in alleviating friction and wear. This work suggests numerous applications for this new solid-state nanolubricant.

Multiwall WS₂ nanotubes of 40-50 nm diameter were functionalized with n-octadecyl phosphonic acid by sonication in toluene and blended with mixtures of polystyrene (PS) and polymethylmethacrylate (PMMA) to form new nanocomposite (NC) materials. The surface and domain structures were studied by atomic force microscopy (AFM), scanning transmission X-ray microscopy (STXM) and transmission electron microscopy (TEM) for various levels of loading of nanotubes up to 20 wt%. Phase-separated domain size and surface roughness of the nanocomposite films were found to be dramatically reduced relative to the pure homopolymer blend and good dispersal of the nanotubes in the blend matrix was attained.

Friction and wear of powder materials impregnated with commercially available layered (platelets) WS₂ (2H) and inorganic fullerene-like WS₂ nanoparticles (IF) were studied. Bronze-graphite, iron-graphite and iron-nickel-graphite samples were used in this experiment. The linear wear of powder materials (in situ) was measured. It was shown that the IF nanoparticles impregnated into the pores improve the tribological properties of powder materials in comparison to a reference sample or the sample impregnated with 2H solid lubricant particles. The mechanisms of friction and wear of the IF nanoparticles have been considered. The tribological role of the wear particles and nanoparticles of solid lubricants has been analyzed in the framework of a third body lubrication model. The state of the IF nanoparticles before and after the wear test was studied. It was found that the shape of the IF nanoparticles is preserved during the friction tests under high loads. Thin wear debris surrounded by spherical IF nanoparticles appear to be formed and provide easily sheared lubrication film (low friction coefficient) during friction experiments of powder materials containing IF nanoparticles.

The Raman spectrum of Cs₂O₂ excited at 632.8 nm shows a single O₂^-2 fundamental band at wavenumber of 742.5 cm^-1 and second and third overtones at 1468.5 and 2176.8 cm^-1, respectively. The harmonic wavenumber ω_e = 759.5 ± 0.7 cm^-1 and anharmonicity constant ω_eχ_e = 8.4 ± 0.3 cm^-1 were calculated directly from the measurements. These results are compared with ω_e = 1151.0 ± 1.5 cm-^-1 and ω_eχ_e = 9.6 ± 0.5 cm^-1 recently found for O₂^- ion in CsO₂ by others. The lower ω_eχ_e of O₂^-2 relative to that of O₂^- indicates a broader (smaller curvature) anharmonic oscillator potential well.

Laser ablation is a powerful technique for producing nanoparticles such as C₆₀. In comparison to high-temperature gas-phase or solid/gas-phase reactions, the laser ablation technique is found to be suitable for the growth of nano-crystals of a specific shape and size. This paper reports on the synthesis, by means of a modified laser ablation technique, of inorganic fullerene-like structures (IF) of NiCl₂, in the form of polyhedral and nanotubes.

Layered metal disulfides-MS₂ (M = Mo, W) in the form of fullerene-like nanoparticles and in the form of platelets (crystallites of the 2H polytype) have been intercalated by exposure to alkali metal (potassium and sodium) vapor using a two-zone transport method. The composition of the intercalated systems was established using X-ray energy dispersive spectrometer and X-ray photoelectron spectroscopy (XPS). The alkali metal concentration in the host lattice was found to depend on the kind of sample and the experimental conditions. Furthermore, an inhomogeneity of the intercalated samples was observed. The product consisted of both nonintercalated and intercalated phases. X-ray diffraction analysis and transmission electron microscopy of the samples, which were not exposed to the ambient atmosphere, showed that they suffered little change in their lattice parameters. On the other hand, after exposure to ambient atmosphere, substantial increase in the interplanar spacing (3-5 Å) was observed for the intercalated phases. Insertion of one to two water molecules per intercalated metal atom was suggested as a possible explanation for this large expansion along the c-axis. Deintercalation of the hydrated alkali atoms and restacking of the MS₂ layers was observed in all the samples after prolonged exposure to the atmosphere. Electric field induced deintercalation of the alkali metal atoms from the host lattice was also observed by means of the XPS technique. Magnetic moment measurements for all the samples indicate a diamagnetic to paramagnetic transition after intercalation. Measurements of the transport properties reveal a semiconductor to metal transition for the heavily K intercalated 2H-MOS₂. Other samples show several orders of magnitude decrease in resistivity and two- to five-fold decrease in activation energies upon intercalation. These modifications are believed to occur via charge transfer from the alkali metal to the conduction band of the host lattice. Recovery of the pristine compound properties (diamagnetism and semiconductivity) was observed as a result of deintercalation.

The impregnation of inorganic fullerene-like nanoparticles of WS₂ (IF) allows to improve effectively the tribological properties of powdered materials in comparison to the impregnation of oil or commercially available layered WS₂ (2H) particles. The main goal of this work was to determine the dominant lubrication regimes under friction of the bronze, iron, and iron-nickel porous matrixes impregnated with 2H and IF solid lubricants. The tribological tests were performed at laboratory atmosphere (humidity Ο50%) using a ring-on-block tester at the sliding speed of V = 1 m/s, and the loads of 150-1000 N. The wear of the metal bodies was measured by an eddy current probe system and by weighting of the samples before and after the test. In order to evaluate the radial clearance, the profiles of wear blocks were analyzed by profile projector. Than these data were used in the calculation of the Sommerfeld reciprocal values. Friction and wear results were presented as the Stribeck curves. The critical Sommerfeld reciprocals were evaluated from these curves. The Stribeck curves were compared with the Morgan's curves for different ranges of non-dimensional permeability, ψ. These results are used then in calculation of the permeability, Φ. Three lubrication regimes as: quasi-hydrodynamic, boundary or mixed, and dry friction were revealed under friction of porous samples in the load-range studied. It was found that the impregnation of IF nanoparticles provides the regime of quasi-hydrodynamic lubrication in the widest range of loads in comparison to the reference sample and the sample impregnated with 2H-WS₂. Fe-Ni samples exhibited the highest wear resistance and provided the widest range of quasi-hydrodynamic lubrication in comparison to bronze and iron powdered composites. The effect of IF on the regimes of lubrication is explained on the base of the third-body model. It is expected that the sliding/rolling of the IF nanoparticles in the boundary of the first bodies and in between the wear particles (third-body) facilitate the shear of the lubrication film and thus provide the quasi-hydrodynamic regime of friction. It is supposed that the roll shape of IF nanoparticles allows to release the IF from the pores to contact surfaces.

WS₂nanotubes were synthesized in large amounts by reaction of H₂S with WO₃ nanopowder using a fluidized-bed reactor. The nanotubes come often in a few centimeter long bundles or alternatively as a few centimeters large foil deposited on the quartz wall of the reactor. Transmission electron microscopy revealed that the open-ended nanotubes are quite uniform in shape: Up to 0.5-mm long and 15-20 nm in diameter, and they are chiral.

In the past few years, inorganic fullerene-like (e.g. IF) supramolecules of metal dichalcogenide MX₂ (M=Mo,W, etc.; X=S, Se), materials with structures closely related to (nested) carbon fullerenes and nanotubes have been synthesized. Recent experiments showed that IF possess lubricating properties superior to those of commercially available layered solid lubricant (2H-WS₂ polytype) in a wide range of operating conditions. It was shown before that the impregnation of a small amount of such nanoparticles into porous bronze matrix largely improve the tribological properties of bronze-steel contact pairs. In the present work, the effect of the PV (pressure-velocity) parameter on the transition to seizure for powdered bronze-graphite, iron-graphite and iron-nickel-graphite composites impregnated 2H and IF lubricant has been studied. The tribological tests were performed using a ring-block tester at loads of 150-1200 N and sliding speeds from 0.5 to 1.7 m/s. It was found that impregnation of IF into the pores improves the tribological properties of the powdered composites in comparison to 2H-WS₂ solid lubricant. Furthermore, it was established that the impregnation of oil together with the IF nanoparticles allows to provide very high load bearing capacity of the powdered materials. It is suggested that the transition to seizure occurs when the wear debrises accumulate in the pores on the surface. This process practically blocks the surface pores and limits the supply of the solid lubricant particles to the contact surface. The main advantage of the IF nanoparticles is attributed to: (a) slow release and supply of nanoparticles from the open pores to the surface; (b) sliding/rolling of the IF between the rubbing surfaces; and (c) prevention of the accumulation of the agglomerated wear particles in the pores. The model of third body was used in order to explain the effect of the wear particles, oil and solid lubricant particles on the friction and wear behavior of powdered composites.

In the past few years, inorganic fullerene-like (IF) supramolecules of metal dichalcogenide WS₂ and MoS₂ with structures closely related to (nested) carbon fullerenes and nanotubes have been synthesized. Recent experiments showed that IF added to oil and impregnated into the porous matrixes possess lubricating properties superior to those of layered WS₂ and MoS₂ (2H platelets). The main goal of this work was to analyze the mechanism of friction of fullerene-like nanoparticles. Friction and wear behavior of IF in different contact conditions is studied. Third body model is considered. Sliding/rolling of the IF nanoparticles in the boundary of the first bodies and in between the wear particles (third body) is supposed to facilitate the shear of the lubrication film. Broken and oxidized 2H-WS₂ small pieces adhered to wear debris do not provide high tribological properties especially under high loads.

We report on the investigation of surface-plasmon excitation of anisotropic WS₂ hollow nanoparticles in a near-field geometry by means of a scanning transmission electron microscope. The shell thickness influence on the electron-energy-loss-spectroscopy spectra is experimentally observed and is analyzed within a classical dielectric formalism. As for the isotropic case, we evidence one symmetric (tangential) and one antisymmetric (radial) mode. We point out the intriguing fact that, for the anisotropic case, one can relate these modes to the interband transition of the in-plane component of the dielectric tensor and to the bulk-plasmon energy of the out-of-plane component.

In the past few years, WS2 and MoS2 nanoparticles (IF) with structures closely related to (nested) carbon fullerenes and nanotubes have been synthesized. It was shown before that addition of a small amounts of such nanoparticles to lubricating fluid largely improve the tribological properties of contact surfaces. In the present work, impregnation of the nanoparticles into a porous powder (bronze-graphite) matrix is demonstrated. The critical point to seizure of the powder matrix impregnated with mineral oil, 2H-WS2 platelets and IF nanoparticles was measured and is 300, 570 and 950 N, respectively. The friction coefficient of the powder matrix lubricated by oil and oil + IF-WS2 was measured. It was found that the addition of the IF nanoparticles in the oil decreased the friction coefficient by 30-50% as compared to the surfaces lubricated by the oil alone. The main effect of TF nanoparticles in comparison to 2H-WS2 platelets appears to be the storage of the nanoparticles for long periods of times within the pores and the gradual release and furnishing to the contact surface. Once released from the pores. IF nanoparticles protect better the rubbed surfaces against straight contact. (C) 2001 Elsevier Science B.V. All rights reserved.

Two methods for the synthesis of CdTe nanoparticles in zirconia sol-gel films are demonstrated. The nanoparticles were obtained by chemical reduction of Te(IV) using reducing agent (hydrazine) or tin chloride. Particle sizes ranging from 6 to 20 nm in diameter could be prepared by varying the experimetal parameters. The size and crystalline structure of the particles were characterized by optical absorption, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. The film morphology was characterized by scanning force microscopy. The film obtained by SnCl₂ method is smooth and homogeneous. The dense structure of CdTe nanoparticles of a few nm in diameter is revealed. The films prepared with hydrazine are porous as a result of evolution of the decomposition gaseous products during the reduction. Advantages and disadvantages of the two methods are discussed.

The inorganic analogs of carbon fullerenes and nanotubes, like MoS(2) and BN, are reviewed. It is argued that nanoparticles of 2D layered compounds are inherently unstable in the planar configuration and prefer to form closed cage structures. The progress in the synthesis of these nanomaterials. and, in particular. the large-scale synthesis of BN, WS(2) and V(2)O(5) nanotubes, are described. Some of the electronic, optical and mechanical properties of these nanostructures are reviewed. The red-shift of the energy gap with shrinking nanotube diameter is discussed as well as the suggestion that zigzag nanotubes exhibit a direct gap rather than an indirect gap, as is prevalent in many of the bulk 2D materials. Some potential applications of these nanomaterials are presented as well, most importantly the superior tribological properties of WS(2) and MoS(2) nested fullerene-like structures (onions).

Recently, pure phases of hollow multi-walled WS₂ nanotubes were prepared from a surface reaction with reduced tungsten oxide nanowhiskers. During the process, which starts with WO_3-x nanoparticles and finishes with WS₂ nanotubes, particular care has been devoted to the evolution of the tungsten oxide cores once the first encapsulating WS₂ layer has been formed. The reduced tungsten oxide phases were previously studied by a combination of techniques, including high-resolution transmission electron microscopy and X-ray diffraction. In the present study, Raman spectroscopy combined with the previous two techniques is used to give further detail concerning the structure of the reduced oxide phases. This study sheds some further light on the reduction process of the tungsten suboxide phases and the growth mechanism of oxide nanowhiskers and subsequently WS₂ nanotubes from quasi-isotropic tungsten oxide nanoparticles.

Inorganic fullerene-like (hollow onionlike) nanoparticles (IF) and nanotubes have attracted considerable interest in recent years, due to their unusual crystallographic morphology and their interesting physical properties. IF-MoS₂ and nanotubes were first synthesized by a gas-phase reaction from MoO₃ powder. This process consists of three steps: (1) evaporation of the MoO₃ powder as molecular clusters; (2) condensation of the oxide clusters to give MoO(3-x) nanosize particles; (3) sulfidization of the suboxide nanoparticles to generate IF nanoparticles. The evaporation of MoO₃ (step 1) and the IF particle formation from the oxide nanoparticles (step 3) have been investigated already, while the mechanism for the suboxide nanoparticles formation (step 2) has not been studied before and is reported here. According to the present model, a partial reduction of the trioxide molecular clusters (3-5 molecules) leads to the formation of MoO(3-x) nanoparticles (5-300-nm particles size) - the precursor for IF-MoS₂. A mathematical model, which takes into account the diffusion of the reactants into the reaction zone, the chemical reactions, and the boundary conditions obtained from the experiments, is established and solved. Based on the comprehensive understanding of the IF-MoS₂ growth mechanism from MoO₃ powder and the solution of the diffusion equations, a gas-phase reactor, which allowed reproducible preparation of a pure IF-MoS₂ powder (50 mg per batch) with controllable sizes, is demonstrated.

Recent progress in the synthesis of bulk quantities of long WS₂ nanotubes has allowed them to be considered as potential candidates in various applications, specifically in nanotechnology. In order to evaluate their efficacy in such applications and to obtain a better insight into their growth mechanism, morphological studies were performed both by scanning electron microscopy and transmission electron microscopy. Three types of WS₂ nanotubes, a few microns in length, were found. The nanotubes denoted "thin" have a diameter up to 30 nm and are circular; those denoted "thick" have a larger diameter, up to 150 nm, and are often polygonal. A third kind of nanotube, bundled or fused, could be also discerned. Differences in the morphology of the nanotube caps were also observed: The majority of "thin" nanotubes exhibit a head close to hemispherical, while the "thick" ones have a peculiar 90° apex. It is argued that the two discernible morphologies are obtained through two distinct growth mechanisms, as discussed in the text.

Thin films molybdenum dichalcogenide, MoS₂, were prepared by cathodic electrochemical deposition from aqueous and non-aqueous solutions of tetrathiomolybdate ions, at different temperatures. The films were X-ray amorphous as deposited. They consist of an amorphous matrix in which quantum sized nanocrystallites or clusters were embedded. Upon annealing at high temperatures, the films obtained from aqueous solutions become crystalline and highly texturized having their van der Waals planes oriented parallel to the substrate, whereas, those obtained from ethylene glycol solutions kept on the amorphous matrix, with slightly larger sizes MoS₂ nanoparticles embedded, than before annealing. Difference in the mechanism of the electrodeposition in aqueous and ethylene glycol solutions is discussed.

The synthesis of a pure phase of very long and hollow WS₂ nanotubes from short but asymmetric oxide nanoparticles is described. In this process, the oxide nanoparticles grow along their longest axis; and subsequently their outermost layer is being sulfidized, while the growing oxide tip remains uncoated as long as the nanowhisker continues to grow. Thereafter, the sulfide cup is closed and a slow diffusion controlled sulfidization of the oxide core is completed within 60-120 min.

Raman and resonance Raman spectra of MoS2 nanoparticles, in the form of inorganic fullerenelike nanoparticles with diameters ranging from 200 to 2000 Angstrom in size, and platelets ranging from 50 to 5000 Angstrom in size, are presented. Off resonance, the first-order Raman bands are broadened, but not significantly shifted, and no additional bands are observed, indicating that the atomic structure is preserved, at least locally, in the nanoparticles. The broadening effect is assigned to phonon confinement by facet boundaries. In the resonance Raman spectra of the nanoparticles, several additional first-order peaks are observed. The electron-phonon coupling responsible for the strong-resonance conditions is identified through dynamic band calculations. Using temperature-dependent resonance Raman measurements, we assign these peaks to zone-boundary phonons activated by disorder and finite-size effects. By analyzing the position of the dispersive peak at 429 (-1) under resonance conditions, it was possible to probe the softening of modes propagating in the c-axis cm direction. [S0163-1829(99)08827-X].

Complex tungsten oxides, consisting of nonstoichiometric oxides of the form WO_3-xand stoichiometric lamellar oxides of the form {001}_RW_nO_3n-1(n=3 to 6) have been observed incorporated within 2H-WX₂(X=S or Se) inorganic fullerene-like (IF) structures by HRTEM. These encapsulates were formed from a gas-solid reaction between H₂Xand disordered WO_3-xprecursors exhibiting a range of particle sizes and morphologies. The microstructures of most of the encapsulated oxides could be described in terms of {hkl}_Rcrystallographic shear (CS) structures formed relative to an ReO₃-type (R) substructure. Smaller spheroidal WO_3-xencapsulates were frequently found to exhibit random {103}_RCS defects of the Wadsley type, while larger, needle encapsulates were found to form exclusively {001}_RW_nO_3n-1type lamellar structures that were predominantely ordered. Spheriodal encapsulates with randomly spaced {001}_RCS planes were also observed encapsulated inside 2H-WSe₂IF structures. The growth and morphologies of the encapsulating 2H-WX₂shells were profoundly influenced by those of the precursor oxides used in their formation. Ordering mechanisms were proposed with respect to the formation of the ordered encapsulated oxides from the disordered precursors.

Recently, inorganic fullerene-like (IF) supramolecules of metal dichalcogenide MX₂ (M = Mo, W, etc.; X = S, Se), materials with structures closely related to (nested) carbon fullerenes and nanotubes have been synthesized. The main goal of the present work was to study the tribological properties of IF-WS₂ in comparison to 2H-WS₂ and MoS₂ platelets over a wide range of loads and sliding velocities. The size and shape distributions of the nanoparticles were studied by transmission electron microscopy (TEM). The average size of the IF-WS₂ particles was 120 nm, while that of 2H-WS₂ and 2H-MoS₂ was 0.5 μm and 4 μm. The chemical reactivity of the different powders in an oxygenated atmosphere was verified by heating the powders in ambient atmosphere. The friction experiments were performed in laboratory atmosphere (humidity ∼ 50%) using a ring-block tester. Complementary information on the state of wear of the powders in the lubricating fluid and on the metal surfaces of the specimens was obtained using a combination of TEM, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It has been established that IF-WS₂ nanoparticles appear to have excellent tribological properties in definite loading range in comparison to typical metal dichalcogenides. The oxidation of the IF particles and the wear track was essentially less than with solid lubricants made of platelets of the same chemical compound (WS₂). The main advantages of IF nanoparticles lie in their round shape and the absence of dangling bonds.

The optical properties of inorganic fullerene-like and nanotube MS₂ (M = Mo, W) material are studied through absorption and resonance Raman, and compared to those of the corresponding bulk material. The absorption measurements show that the semiconductivity is preserved. Nevertheless, the positions of the excitons are altered in comparison to the bulk. The Raman spectra of the nanoparticles show a close correspondence to that of the bulk. However, the first-order peaks are broadened and, under resonance conditions, new peaks are observed. The new peaks are assigned to disorder-induced zone edge phonons.

Recently, a model for the growth mechanism of inorganic fullerene-like (IF) nanoparticles of MS₂ (M = Mo, W) from the respective oxides was presented (Feldman, Y.; Frey, G. L.; Homyonfer, M.; Lyakhovitskaya, V.; Margulis, L.; Cohen, H.; Hodes, G.; Hutchison, J. L.; Tenne, R. J. Am. Chem. Soc. 1996, 118, 5362). According to this model, sulfidization of oxide particles of 3 powders suggests the occurrence of a unique driving force for the fast growth of the first curved sulfide layer (001) around an oxide nanoparticle. According to the present model, a synergy between the reduction and sulfidization processes which occurs in a very narrow window of parameters leads to the formation of the first one or two closed sulfide layers. The present study is not limited to the sulfides. The formation of IF-WSe₂ (Tsirlina, T.; Feldman, Y.; Homyonfer, M.; Sloan, J.; Hutchison, J. L.; Tenne, R. Fullerene Sci. Technol. 1998, 6, 157) is found to be consistent with the same kind of model.

With their unique chemical stability and high electron mobility, boron-doped thin diamond films are likely to have favorable properties for a number of electrochemical applications. A review of the recent developments in this field is presented with critical evaluation of the experimental data. In particular, the relationship between the material's characteristics and the electrochemical behavior of the electrodes is discussed in detail. A number of potential applications for these electrodes are presented: for dimensionally stable electrodes in highly corrosive environments, for discharging toxic effluents, and for electrochemical sensors.

Optical-absorption spectroscopy of inorganic fullerenelike (Formula presented) and (Formula presented) ((Formula presented) and (Formula presented)) is reported in the range 400-800 nm, at temperatures between 4-300 K, and compared to the corresponding bulk (2H) material. A systematic study of the effect of IF size and number of atomic layers on the optical properties shows that the semiconductivity of the layered material is preserved in the IF structures. Nevertheless, all IF with number of layers (Formula presented) exhibit a decrease in the (Formula presented) and (Formula presented) exciton energies. This redshift becomes larger as additional inner layers are formed, until a saturation value is reached (Formula presented) We assign this redshift to the deformations, curvature, and discommensuration between adjacent atomic layers the structure must accommodate in order to form an IF structure. An increase in the exciton energies is observed in IF consisting of a few sulfide layers (Formula presented) This blueshift is attributed to a quantum confinement in the (Formula presented) direction. Band-structure calculations show that an expansion of (Formula presented) along the (Formula presented) axis leads to a convergence of the levels (Formula presented) and (Formula presented) which is displayed in the absorption spectra of IF with 1 or 2 layers.