Danielle Slomberg

Addressing the complexity of water chemistry in environmental fate modeling for engineered nanoparticles.

Engineered nanoparticle (ENP) fate models developed to date - aimed at predicting ENP concentration in the aqueous environment - have limited applicability because they employ constant environmental conditions along the modeled system or a highly specific environmental representation; both approaches do not show the effects of spatial and/or temporal variability. To address this conceptual gap, we developed a novel modeling strategy that: 1) incorporates spatial variability in environmental conditions in an existing ENP fate model; and 2) analyzes the effect of a wide range of randomly sampled environmental conditions (representing variations in water chemistry). This approach was employed to investigate the transport of nano-TiO2 in the Lower Rhône River (France) under numerous sets of environmental conditions. The predicted spatial concentration profiles of nano-TiO2 were then grouped according to their similarity by using cluster analysis. The analysis resulted in a small number of clusters representing groups of spatial concentration profiles. All clusters show nano-TiO2 accumulation in the sediment layer, supporting results from previous studies. Analysis of the characteristic features of each cluster demonstrated a strong association between the water conditions in regions close to the ENP emission source and the cluster membership of the corresponding spatial concentration profiles. In particular, water compositions favoring heteroaggregation between the ENPs and suspended particulate matter resulted in clusters of low variability. These conditions are, therefore, reliable predictors of the eventual fate of the modeled ENPs. The conclusions from this study are also valid for ENP fate in other large river systems. Our results, therefore, shift the focus of future modeling and experimental research of ENP environmental fate to the water characteristic in regions near the expected ENP emission sources. Under conditions favoring heteroaggregation in these regions, the fate of the ENPs can be readily predicted.

A network perspective reveals decreasing material diversity in studies on nanoparticle interactions with dissolved organic matter

Significance Understanding the environmental fate of engineered nanoparticles (ENPs) is essential to the risk assessment of nanotechnology. Dissolved organic matter (DOM) strongly influences the behavior of ENPs in aqueous systems. This influence depends on many factors and, in particular, the types of ENPs and DOM. Accordingly, recent reviews have called repeatedly to expand the range of DOM and ENPs studied. Here, we use a network perspective to assess, in terms of the material types studied, the current state of research into DOM–ENP interactions. We identify global tendencies in the choice of materials and experimental approaches that have contributed to an undesirable discrepancy between the ever-increasing number of published experiments and the persisting call for investigation of more material types. Dissolved organic matter (DOM) strongly influences the properties and fate of engineered nanoparticles (ENPs) in aquatic environments. There is an extensive body of experiments on interactions between DOM and ENPs and also larger particles. [We denote particles on the nano- and micrometer scale as particulate matter (PM).] However, the experimental results are very heterogeneous, and a general mechanistic understanding of DOM–PM interactions is still missing. In this situation, recent reviews have called to expand the range of DOM and ENPs studied. Therefore, our work focuses on the diversity of the DOM and PM types investigated. Because the experimental results reported in the literature are highly disparate and difficult to structure, a new format of organizing, visualizing, and interpreting the results is needed. To this end, we perform a network analysis of 951 experimental results on DOM–PM interactions, which enabled us to analyze and quantify the diversity of the materials investigated. The diversity of the DOM–PM combinations studied has mostly been decreasing over the last 25 y, which is driven by an increasing focus on several frequently investigated materials, such as DOM isolated from fresh water, DOM in whole-water samples, and TiO2 and silver PM. Furthermore, there is an underrepresentation of studies into the effect of particle coating on PM–DOM interactions. Finally, it is of great importance that the properties of DOM used in experiments with PM, in particular the molecular weight and the content of aromatic and aliphatic carbon, are reported more comprehensively and systematically.

Insights into natural organic matter and pesticide characterisation and distribution in the Rhone River

Thorough characterisation of natural organic matter (NOM) in natural surface waters remains vital for evaluating pollutant dynamics and interactions with NOM under realistic environmental conditions. Here, we present the characterisation of NOM and pesticide compositions for nine sampling sites over the length of the Rhone River, also evaluating the advantages and limitations of different analytical techniques to determine how they complement one another. Together with dissolved and particulate organic carbon analyses, the dissolved organic matter (DOM, <0.8 mu m) or NOM (unfiltered organic matter) was characterised with gel permeation chromatography, the polarity rapid-assessment method, excitation-emission matrix fluorescence, and pyrolysis-gas chromatography-mass spectrometry to evaluate both composition and distribution. An additional objective was the determination of the NOM degradation state (i.e. constantly produced autochthonous or weakly degraded allochthonous species), an important factor in assessing potential NOM-pollutant interactions. The NOM compositions (i.e. proteins, polyhydroxy aromatics, polysaccharides, amino sugars) and proportions were similar between sites, but variations were observed in the relative proportions of autochthonous and allochthonous material from north to south. Anionic proteins and polyhydroxy aromatics in a molecular weight range of similar to 1000-1200 Da comprised the majority of the DOM. As a pollutant case study, five pesticides (glyphosate, metalochlor, chlortoluron, isoproturon, propyzamide) and some of their metabolites (aminomethylphosphonic acid, metolachlor ethanesulfonic acid and metolachlor oxanilic acid) were measured. Several exhibited trends with the NOM, particulate organic carbon and suspended particulate matter distributions in the Rhone waters, suggesting a significant influence on pesticide fate and transport in the river.

Characterisation of suspended particulate matter in the Rhone River: insights into analogue selection

Environmental context The fate and behaviour of pollutants such as pesticides, metals and nanoparticles in natural waters will influence their effects on the environment and human health. Owing to the complexity of natural waters and suspended particulate matter (SPM) that can interact with pollutants, as well as low pollutant concentrations, determination of pollutant fate and transport is non-trivial. Herein, we report a characterisation of the Rhone River chemistry to provide insight into selecting SPM analogues for experimental and modelling approaches. Abstract Selection of realistic suspended particulate matter (SPM) analogues remains vital for realising representative experimental and modelling approaches in predicting the environmental fate of pollutants. Here, we present the characterisation of dissolved-ion and SPM compositions for nine sampling sites over the length of the Rhone River. Dissolved-ion concentrations remained stable, but SPM concentrations varied among sampling sites. Size fractionation and mineralogical characterisation of the SPM revealed that the same minerals (e.g. quartz, calcite, muscovite) constituted every size class from 0.5 to >50µm, as is usually found with allochthonous and large-scale systems. To gain insight into SPM analogue selection, aggregation kinetics of silica, calcite, muscovite, feldspars and clays were monitored in the native filtrate and related to the respective zeta potentials (ζ). An SPM mixture of calcite (49%), muscovite (14%), feldspar (23%) and chlorite (14%) proved the best match for the Rhone SPM, demonstrating that mineral surface chemistry, structure and size are all important in selecting a realistic SPM analogue for a riverine system.

The influence of past research on the design of experiments with dissolved organic matter and engineered nanoparticles

To assess the environmental fate of engineered nanoparticles (ENPs), it is essential to understand their interactions with dissolved organic matter (DOM). The highly complex nature of the interactions between DOM and ENPs and other particulate matter (PM) requires investigating a wide range of material types under different conditions. However, despite repeated calls for an increased diversity of the DOM and PM studied, researchers increasingly focus on certain subsets of DOM and PM. Considering the discrepancy between the calls for more diversity and the research actually carried out, we hypothesize that materials that were studied more often are more visible in the scientific literature and therefore are more likely to be studied again. To investigate the plausibility of this hypothesis, we developed an agent-based model simulating the material choice in the experiments studying the interaction between DOM and PM between 1990 and 2015. The model reproduces the temporal trends in the choice of materials as well as the main properties of a network that displays the DOM and PM types investigated experimentally. The results, which support the hypothesis of a positive reinforcing material choice, help to explain why calls to increase the diversity of the materials studied are repeatedly made and why recent criticism states that the selection of materials is unbalanced.

Optimizing the properties of TiO2 nanomaterials used as UV-blockers in sunscreen to maximize the efficiency and safety of the final product

O to excellent heat resistance and physical properties (especially, impact strength), as well as transparency, Polycarbonates (PC) have been used widely in various applications such as electronics, construction materials and automotive components. Certain applications such as product exterior casings for electronics and headlamp reflectors require additional heat resistance due to their constant exposure to heat. We, at Samyang Corp., developed new oligomer structures consisting of polyester compounds along with its synthesizing technique. We synthesized the oligomers with varying molecular weights by altering the experimental conditions and investigated the mathematical relationships between the experimental conditions and the molecular weight of the oligomer. These novel oligomers exhibit high heat resistance due to its rigid structure; moreover, a block copolymer containing the polyester oligomer along with polycarbonate features a higher heat resistance capability compared to the regular PC.T metallic nanostructure has the physical properties as remarkable increase in surface-to-volume ratio and the development of nanostructure fabrication has revolutionized many applications ranging from electronics to photonics, information strage and sensing, as well as energy conversion and storage. Electrochemical Migration (ECM) is known as a cause of invoking insulation deterioration on the printed circuit board in high-humid and high temperature environment. Although a considerable number of studies have been reported on suppressing ECM, utilization using ECM has not really been studied so far. The previous studies of suppressing reveal that eluting metal grows as dendrites. Recent years, the concern with utilization using ECM has been growing because ECM is the low cost and green fabrication technique and the reaction is caused by DC voltage and water. The attempt has been made at fabricating the metallic nanostructure using ECM. However, it has reported that ECM stops during growth of dendrites between electrodes because dendrites form short circuit. Thus, the sustainable and large-scale fabrication for the metallic nanostructure has not been established. The purpose of this study is to demonstrate sustainable and large-scale fabrication for the metallic nanostructure using ECM. In this study, we changed experimental conditions and evaluated these results.D graphene growth on functional substrates via chemical vapor deposition is an attractive approach to manufacturing flexible electronic devices, as it avoids the drawbacks of transferred graphene. To fabricate flexible devices on plastic substrates, the growth temperature must be below ~200 °C to prevent substrate deformation. Here, we report the direct growth of wrinkle and defect-free graphene on flexible substrates at low temperatures and without transfer processes. We show that defect-free graphene can be directly grown on a variety of substrates via the introduction of an ultra-thin titanium buffer layer, due to perfect lattice matching between titanium and carbon atoms. We further show that ex situ Ti layers (TixOy) with a thickness of ~10 nm does not influence the transmittance or electrical conductivity of functional substrates. We report theoretical and experimental evidence for large-scale (4×4 cm2) high-quality graphene grown on in situ deposited titaniumbuffered substrates at 150 °C in a CH4/H2 atmosphere via plasma-assisted thermal CVD. We applied the proposed methodology to fabricate flexible and transparent thin-film capacitors with direct grown topand bottom-graphene electrodes. These findings could pave the way to the practical exploitation of flexible electronic devices via large-scale high-quality monolayer graphene grown directly with no transfer processes.G Oxide (GO) is a novel low-cost material, presenting intriguing proprieties. Obtained by oxidation of graphite, graphene oxide is a hydrophilic and so water-soluble biocompatible compound, making it the perfect candidate in the design of nanocarriers. The presence of hydroxyl, epoxy and carboxyl groups on its surface enables its easy functionalization and high loading capacity (circa 200% in some cases). In addition, it presents photo-thermal activity, which means it is able to convert light absorbed into heat. Photo-Thermal Therapy (PTT) is an emerging discipline envisaged for Cancer and Antibiotic treatments. The photo production of cytotoxic species, known as Photodynamic Therapy (PDT), presents several advantages, such as good spatiotemporal release control, fast reaction rates and the absence of residues after the reaction. Nitric Oxide (NO) is an example of those species, which can have beneficial or deleterious effect, depending on the concentration. This short half live radical presenting reduced distance diffusion in cellular environment does not suffer Multidrug Resistance (MDR). Here resides the interest of combining light-controlled NO release with suitable nanocarriers. Covalent link of a nitro-aniline derivative nitric oxide photo donor to nanoGO results in a bimodal nanoplatform that combine light-controlled NO release with photo-thermal proprieties.T polyoxazolines is an attractive polymers family characterized by a pseudo-peptidic structure, own bio and hemocompatibility, low toxicity and furtivity towards immune systems-basic properties for biomedical applications. They offer an additional attraction with the ability to self-assembly under various morphologies including spherical nanoparticles, nanowires using hydrogen bonds, dipolar interactions, etc. In this study, we focused on poly (2-methyl-2-oxazoline) decorated by coumarin units, able to photo-activity and able to pi-stacking and further original self-assemblies as already shown with peptides. In a previous work, we demonstrated the UV-activity and the self-organization of amphiphilic di-block and triblock co-polyoxazolines in water. Herein, well-defined single strand helicoidal fibers were elaborated using amphiphilic graft copolymers. These polymeric filo micelles grow according to Crystallization-Driven Self-Assembly (CDSA) between polyoxazoline repetitive units and the coumarin ones. In other experimental conditions, the UV-activity of spherical nanoparticles of the same copolymers were also examined particularly the photo-cross-linking of the nanoparticle core.I recent years, frequent occurrence of cyanobacteria bloom has disrupted the balance of lakes and reservoirs around the world. Copper-Core Carbon-Shell Nanoparticles (CCCSNPs), as a novel material, have showed a good antibacterial and anti-mildew performance in previous study. In this study, we tried to demonstrate the potential effect of CCCSNPs on cyanobacterium Microcystis aeruginosa growth and clarify the mechanism to know the application prospects of the material in controlling cyanobacteria bloom. Compared with the widely used algaecides CuSO4, CCCSNPs significantly reduced chlorophyll a content of M aeruginosa when the concentration of Cu2+ in the medium was the same as the CuSO4, so the inhibitory effect of CCCSNPs on algae was better and lasted longer than that of CuSO4. We further explored the mechanism of inhibitory effect, finding that intracellular excess Reactive Oxygen Species (ROS) were produced after exposure to CCCSNPs, which were 2.4 and 1.5-fold higher than the control and the CuSO4 treatment, respectively. Excess ROS formation caused oxidative damage to algae and reduced the photosynthetic efficiency, which further inhibited algal growth. Therefore, it is reasonable to propose that CCCSNPs could induce excess ROS production and further interfere with algal photosynthesis to achieve a satisfactory effect with a longer action time.T ability of lanthanide ions to generate fascinating Near-Infrared (NIR) emissions has played important roles in optical fiber communication, semiconductor optoelectronic devices, biomedical imaging and bioanalyses. Two aspects of my group’s recent works on the lanthanide activated advanced materials and nanotechnology will be introduced. Firstly, we have developed various lanthanide doped nanocrystals for photonic and biological applications. For instance, biosensors with both high sensitivity and rapid response are greatly desired for enabling rapid and sensitive detection of various virus gene in a cost-effective way. We have developed lanthanide doped up-conversion nanoprobe/nanoporous membrane to form a heterogeneous assay. Compared to the homogeneous assay, the limit of detection in the heterogeneous assay is significantly improved. Secondly, the ultimate goal of making nanoscale electronic and optoelectronic devices greatly stimulates atomically thin material and heterostructure research. We have introduced lanthanide dopants into two-dimensional (2D) layered semiconductor nanosheet hosts and realize NIR-to-NIR down and up-conversion photoluminescence. Importantly, the luminescence of 2D materials simply pumped by a single NIR laser diode can be extended to a wide range of NIR spectrum, including telecommunication range at 1.55 μm. By considering the abundant energy levels arisen from lanthanide ions, our works open a door to greatly extend and modulate the luminescence wavelengths of 2D semiconductors, which will benefit for not only investigating many appealing fundamental issues, but also developing novel nanophotonic devices.T electronics market had a strong driving force and tendency for developing portable and wearable electronic devices has stimulated the research interests in flexible, renewable and sustainable energy sources. Poly(vinylidene difluoride) (PVDF) is a pyroelectric and piezoelectric polymer and widely investigated for flexible electronics because of its high flexibility, biocompatibility and simplicity of production. A pyroelectric material such as PVDF can effectively convert thermal energy into a temporary voltage when they are heated or cooled. If the temperature stays constant at its new value, the pyroelectric voltage gradually disappears due to leakage current. Thus, a new heating technique such as light irradiation is important to replace the traditional conductive heating method and leads to the poor thermal conductive PVDF polymer with repeatedly fast heating and cooling behavior. A highly effective photo-thermal conversion material reduced tungsten oxide (WO2.72), having the temperature change of 60 °C within 30 seconds under infrared light radiation (IR) was developed in our research group. Therefore, it is highly interesting to study the pyroelectric response of the electrospun PVDF nanofibrous membranes incorporated with efficient photo-thermal conversion material (WO2.72) under IR radiation. In this study, a novel flexible pyroelectric power generator was developed by electrospun PVDF nanofibrous membranes incorporated with various weight fractions of WO2.72 powders. The effects of WO2.72 and electro-spinning (ES) parameters on the crystal structure and pyroelectric properties of PVDF/WO2.72 nanofibrous membranes were examined. Results show that ES effectively induced the β-phase of PVDF and the fraction of β-phase was further increased from 79% to 84% after adding with 7 wt% WO2.72. Besides, the temperature of electrospun PVDF/WO2.72 nanofibrous membrane increased rapidly and reached 98.7 °C from room temperature while pure PVDF nanofibrous membranes only reach to 60.5 °C after 300 seconds under IR radiation. It demonstrated that WO2.72 presents excellent photo-thermal conversion characteristics due to the presence of free electrons or oxygen-deficiency-induced small polarons. As for the pyroelectricity measurement, the PVDF/WO2.72 nanofibrous membranes were sandwiched between two electrodes and the output voltage was measured by repeated heating and cooling process. Controlling by IR radiation, the temperature of the as received PVDF pyroelectric unit with WO2.72 was increased from room temperature to 51.6 °C during heating process and then rapidly cooled down to 29.9 °C within 3 minutes. When the temperature change is 21.7 °C, the maximum output voltage of the pyroelectric unit with WO2.72 reached to 80 mV which is largely enhancement compare to 30 mV of the unit without WO2.72 with 10.1 °C temperature change. Hence, the PVDF/WO2.72 with higher temperature change induces stronger pyroelectric response than pure PVDF sample. In addition, the PVDF/ WO2.72 also shows good stability and durability of pyroelectric power output.P Fluoride (PVDF) is a popular piezoelectric polymer because of its high flexibility, biocompatibility and simplicity of production. These features make PVDF attractive in energy conversion applications between mechanical force and electrical power, such as strain sensors, mechanical actuators and energy harvesters. The aforementioned applications rely on the piezoelectric property of PVDF and it is well-known that appropriate mechanical stretching and electrical polarization are essential factors to achieve good piezoelectricity. Electro-spinning processes can provide PVDF fibers mechanical stretching and electrical poling simultaneously and produce ultrafine and well-distributed nanofibers. Furthermore, previous studies discovered that the nanoparticles addition such as carbon nanomaterials or metallic nanoparticles could help improving the β content of the electrospun PVDF nanofibers. In this study, a rotation drum was used to collect aligned PVDF nanofibers during the electro-spinning process. The aligned fiber membranes were collected by changing the electro-spinning parameters of the rotating speed and the applied voltage. The PVDF nanofiber membranes collected by rotating drum showed higher β content and better mechanical property than the membranes collected on a fixed copper grid collector. The results showed that the orientation and contents of β phase of the aligned nanofiber membranes were both increased with the rotating speed and the applied voltage during the electro-spinning process. The β content of the PVDF fiber membrane reached to 87% at rotating speed of 3000 rpm and applied electric field of 1500 V/cm. Moreover, the aligned PVDF nanofibers with Carbon Nanotubes (CNTs) addition exhibited enhanced β phase content. The received PVDF nanofiber membranes were loaded and evaluated by three types of dynamic mechanical forces: Compression, tensile and bending. According to the different types of the mechanical loading, corresponding piezoelectric units were circumspectly designed. The piezoelectric response (electrical output voltage) of the PVDF nanofiber membranes increased linearly with the applied forces and showed good stability during the cyclic loading.T understand and modify the nonlinear optical properties of transition metal dichalcogenides, TMDs, two-dimensional layered materials are very important research topics nowadays as they can serve as building block for developing next generation high performance micro optics and photonic devices. These materials are very compact with atomic thick layer and have natural band-gap so they can provides strong interaction with light and other favorable features e.g. broadband absorption, transparent and high carrier mobility etc. WS2, which is a typical TMDs material, has layer number depending band gap energy. The WS2 band gap energy and optical properties can be modified by varying their size, layer number and structures. The WS2 nanomaterials and film in various size, layer number or film thickness are fabricated by two methodsultrasounds and sputtering. The nonlinear optical properties of different samples are then studied by using z-scan technique. We have successfully demonstrated some viable methods to tune the nonlinear absorption properties of WS2. We also use the fabricated WS2 film within the diode pumped solid state Nd:YVO4 crystal laser to generate pulsed laser output. A stable pulsed laser operation is achieved by using the fabricated WS2 saturable absorber. The average output power obtained is 19.6 mW (135 kHz). These research findings indicate strong nonlinear optical properties of WS2 and high potential for nonlinear optical devices.S materials, that can change structures and/or physical-chemical properties by active or passive control, has potential applications in energy engineering. They can be used to design cute and efficient energy converting systems, e.g., waste heat generation systems made of Shape-Memory-Alloys (SMA). The advances of electronic and aerospace engineering calls for more robust thermal management technologies that can help the devices to discharge intensive heat release and mitigate the temperature fluctuation. To this end, smart materials can take their inherent advantages in heat transfer enhancing and in providing extra measures for driving coolant flow. In our latest studies, a novel deformable structured surface was fabricated by SMA for the enhancement of boiling heat transfer. Pool boiling heat transfer on deformable structures were performed in three fluids (ethanol, FC-72, water) with different thermal properties was explored. Comparing heat flux versus wall superheat and HTC at different fluxes with fixed geometry, it is found that deformable structure combines the merits of closed-tunnel and open-tunnel. At low heat fluxes, it can increase the numbers of nucleation sites inside the closed tunnels with bent fins and after recovering with open tunnels, the nucleation sites are activated and the bubble growth and departure is accelerated to enhance the HTC significantly. On the other hand, by choosing the appropriate time and opportunity for different fluid to open the tunnels, the deformable structures can be used to achieve adaptive-control of boiling heat transfer. In another study, researchers from POSTECH proposed a smart TiO2-Coated Surface (TCS) for boiling heat transfer. The surface changes its wettability with temperature. Measurement of the contact angle of a water droplet on the tested surfaces after heat treatment showed a wettability increase of TCS, a contact angle reduction from 83.1o to 32.7o when the heat treatment temperature changed from 100oC to 200oC, in other words, TCS is hydrophobic at a low wall temperature and becomes hydrophilic as the wall temperature increases. Hydrophobicity of TCS at low wall temperatures. The TCS improved both the heat transfer coefficient near the boiling inception point at low heat flux regime and critical heat flux at high wall temperatures. People are also developing heat transfer devices that have SMA self-driven unit for flow circulations that working with temperature differences. The study on energy harvesting and thermal management by use of smart materials is a quite young interdiscipline research field, which is still in the initial stage. This presentation gives a critical review to the latest pioneering work. By summarizing the advancements, we propose some comments on the principles and prospect for the future development.D attachment is one of the most important processes in the packaging of power semiconductor devices. Sintered silver has demonstrated superior properties in microelectronic packaging as compared to the traditional solders and conductive epoxies. The sintering joints formed by atomic diffusion of silver nanoparticle can be processed at a temperature significantly lower than the melting temperature of the bulk and can be used for high temperature applications. The potential advantages such as high temperature stability, high electrical and thermal conductivity, good mechanical properties etc. makes silver nanoparticle a promising candidate for die-attach applications. In the present invention, we have synthesized capped silver nanoparticle and nanosilver paste which can be used for pressure-less die attach applications. The percentage of capping according to thermo-gravimetric analysis is around 1%. TEM reveals the size of the silver nanoparticle to be around 3 nm to 80 nm. The heterogeneous particle sizes help in sintering of the nanoparticle at a faster rate because of their large point of contact between each other which also leads to good packing fraction. The die attach paste made from these heterogeneous size silver nanoparticles is used for pressure-less die attach applications on different metallized substrate (Au, Ag and Cu) to achieve a joint strength of 25-30 MPa when sintered at 180oC for 60 minutes. The thermal conductivity of the sintered material was around 200 W/m.K. The above results clearly show that the nanosilver paste sintered at lower temperature has a slight edge over the traditional solder and conductive epoxies.T tribology community presently relies on phenomenological models to describe the various seemingly disjointed steadystate regimes of metal wear. Pure metals such as gold-frequently used in electrical contacts, exhibit high friction and wear. In contrast, nanocrystalline metals, such as hard gold, often show much lower friction and correspondingly low wear. The engineering community has generally used a phenomenological connection between hardness and friction/wear to explain this macro-scale response and thus to guide designs. We present the results of recent simulations and experiments that demonstrate a general framework for connecting materials properties (i.e., microstructural evolution) to tribological response. We present evidence that the competition between grain refinement (from cold working), grain coarsening (from stress-induced grain growth) and wear (delamination and plowing) can be used to describe transient and steady state tribological behavior of metals, alloys and composites. We will explore the seemingly disjointed steady-state friction regimes of metals and alloys, with a goal of elucidating the structure-property relationships, allowing for the engineering of tribological materials and contacts based on the kinetics of grain boundary motion.W can learn how nature produces hierarchical micro-nanostructures for realization of specific functions. Superb mechanical properties as well as unique optical properties can be distinguished examples. These examples have inspired researchers to develop and design new artificial materials. Structural organization with parallel stacking of nanosheets was found in internal structure of nacre of abalone shell and it presents strong and tough mechanical properties. On the other hand, the vertically orientation of nanostructures are also ubiquitous in biocomposites such as teeth and seashells. In this presentation, two types of nanocomposites will be presented, planar shaped nanocomposites with silica layer and vertically oriented nanocomposites with ZnO nanopillars. We demonstrated that 2D and 3D structural organization of nanomaterials can show enhancements of mechanical properties which can exceed limit of conventional nanocomposites.C Nanotubes (CNTs) have received great attentions with their extraordinarily fascinating behaviors such as structural, mechanical, optical and electrical properties. They can be added into various polymers as fillers to prepare advanced functional polymeric composites. However, due to their intrinsically poor dispersibility, achieving a uniform dispersion is generally difficult. As one of the effective methods, milling processes are introduced to reduce the original size of the nanotubes to improve dispersion, especially in the case of CNT suspension rheology for potential battery applications. With interesting functionalities under external fields implying typical flow fields of laminar flow with most cases of rheological aspects and electrical and magnetic fields, electro-responsive Electro-Rheological (ER) characteristics of polymer/CNT composite systems from material rheological viewpoint are examined for various CNT composite particles with polystyrene and PMMA. Interesting characteristics of their ER suspensions include yield stress, flow curve behavior and dielectric analysis. As for Magneto-Responsive Magneto-Rheological (MR) materials, we coated the surface of soft-magnetic carbonyl iron particles with CNT along with polymers to produce their favorable core-shell structure with apparently decreased particle density for better dispersion and then characterized their MR characteristics under magnetic fields applied.F and foldable electronic components require materials that can retain their electrical conductivity even after hard mechanical manipulations and multiple folding events. Such a material was realized with two different methods exploiting the combination of all-biodegradable components (substrate and the polymer matrix) and graphene nanoplatelets (GnPs). A fibrous cellulose substrate was sized with a biopolymer-GnPs conductive ink rendering it electrically conductive (sheet resistance ≈10 Ω/sq). The obtained nanocomposites can be used as electrodes for surface electromyography and for terahertz electromagnetic interference shielding. With a similar approach, a flexible cotton-GnPs conductive nanocomposite was realized. This material addresses several drawbacks related to durability and washability of wearable electronics material. Micro-cracks formed after repeated folding-unfolding events can be healed through a hot-pressing process. Such cotton based conductive composites could find several applications in smart textile industry.P of inks with proper viscoelasticity is the key pre-requirement for extrusion based 3D printing. Here, extrusion based 3D printing Graphene Oxide (GO)/Geopolymer (GOGP) nanocomposite was reported for the first time. We found that, the addition of GO in geopolymeric aqueous mixture (alumio-silicate and alkaline-source particles) dramatically changes its rheology properties and enable the 3D printing that cannot be realized solely by geopolymer, indicating a strong GO/ alumio-silicate interaction. We proposed a model, in which a water layer is laminated between GO and alumio-silicate, based on the facts that both of GO and alumio-silicate are hydrophilic and negatively charged, to account for such phenomenon. The chemical and microstructure analysis showed that the GO nanosheets anchor themselves around and encapsulate individual geo-polymer grains to resist being pullout and at the same time, form a continuous 3D network throughout the whole nanocomposites, which was proved by selective etching of geo-polymer and left behind free-standing porous GO aerogel. Therefore, not only the mechanical properties of geo-polymer were significantly increased by GO, but also very high electrical conductivity was obtained after sintering and endow our 3D printing nanocomposite among the highest conductive ceramic nanocomposites. In addition, we found that, enhancing mechanical properties at material level by employing large GO nanosheets, will inevitably switch failure model from stretching/compression to buckling instability, thus limit the fully exploitation of material properties and thus in turn, structural performance. This finding suggests the local modification of 3D printed structures, especially weakening the rotational stiffness of nodes, is critical for the realization of 3D printing superstrong cellular solid.F more than two decades, many researchers have focused on Carbon Nanotubes (CNTs) which have the superior electrical, thermal and mechanical properties, motivating their use in composites as a fibrous reinforcing agent. Although mechanical properties of CNT reinforced composites have been widely studied, only a few groups have reported strengthening effects for the composites. Before the utilization of CNTs becomes mainstream, it is necessary to develop protocols for tailoring the material properties, so that composites and devices can be engineered to given specifications. In this presentation, we review our recent studies, in which we investigate the nominal tensile strength and strength distribution of Multi-Walled CNTs (MWCNTs) synthesized by the CVD method, followed by a series of high-temperature annealing steps. The structuralmechanical relationships of such MWCNTs are investigated through tensile-loading experiments with individual MWCNTs, Weibull-Poisson statistics, Transmission Electron Microscope (TEM) observation and Raman spectroscopy analysis. The comparatively low value of the shape parameter for MWCNTs resulted from the irregular nanotube structure, which reflects a larger tube defect density relative to conventional fiber materials. Nonetheless, the MWCNTs with an intermediate level of crystallinity produced complete fracture of nanotube walls and exhibited higher nominal tensile strength, suggesting that improvements to the nominal tensile strength of MWCNTs might be achieved by inducing appropriate interactions between adjacent nanotube walls to enable sufficient load transfer to the MWCNT inner layers. This effect should be balanced to permit an adequate load transfer between the inner and outer walls to give clean break fractures.Eng Sanit Ambient | v.24 n.4 | jul/ago 2019 | 833-842 ABSTRACT A set of experiments were carried out in order to establish and evaluate the potential of activated carbon, produced from coffee waste in adsorption process, in the depuration of landfill leachate. Different reagents were studied in the activation of carbon: HCl, HCl + H 2 O 2 , H 3 PO 4 , H 3 PO 4 + H 2 O 2 , all with an impregnation rate of 1:1. The activated carbon that showed the best global results was activated with H 3 PO 4 , obtaining a 51.0, 32.8, 66.0, 81.0 and 97.1% elimination of chemical oxygen demand, ammonia, total chlorine, bromine and copper, respectively. This activated carbon has a total pore area of 4.85 m/g and a median pore diameter of 65.32 micrometers. When different loads of this carbon were placed in a stirrer system in contact with landfill leachate, with the aim of evaluating the effect of the adsorption load and contact time, the concentration of ammonia decreased from the beginning of the adsorption process to the end of it, and the removal of ammonia increased with the increase in the adsorbent load. However, the trend of the amount adsorbed per unit mass decreased with increased dosage. The model Freundlich equilibrium isotherm fits experimental data adequately, giving R values of 0.95, 1/n of 0.5183, and a K value of 7.08*10 L/g, being favourable for adsorption process.

Investigations into titanium dioxide nanoparticle and pesticide interactions in aqueous environments

The influence of three pesticides (glyphosate, aminomethylphosphonic acid (AMPA) and 2,4-dichlorophenoxyacetic acid (2,4-D)) on the colloidal fate of TiO2 nanoparticles (NPs; anatase and rutile) has been investigated under aqueous conditions of variable chemical composition (Na+ or Ca2+), ionic strength (IS, 10−4–10−1 M), and pH (5 or 8). Sorption and degradation of these pesticides in the presence of the NPs were evaluated. In the absence of the pesticides, increasing IS, the presence of the divalent cation Ca2+ and a pH value close to the NP isoelectric point favored NP homoaggregation as expected. However, at low IS (≤10−2 M in NaCl; ≤10−3 M in CaCl2), in the presence of a few μg L−1 of glyphosate and rutile in the mg L−1 range, NP homoaggregation was prevented, despite the pH = 5 close to the NP isoelectric point (4.0–4.2). The phosphonate group of the pesticide drove glyphosate adsorption onto the NP, while the carboxylic group was responsible for the electrostatic stabilization of the NP. The stabilizing effect of glyphosate on NP aggregation however appears to be temporary. Furthermore, TiO2 NPs also adsorbed AMPA and promoted degradation of glyphosate to AMPA. These results highlight new evidence of NP–pesticide interactions and the differences in their fate and potential co-migration behavior in aquatic environments.