Packing Of Nanoparticles Research Articles

Flexible Sers-Active Substrates Based on Silver Nanoparticles Grown in Poly(Acrylic Acid) Grafted to a Polypropylene Film

Flexible SERS substrates were obtained by the photo-activated synthesis of silver nanoparticles in a thin (10–170 nm) layer of poly(acrylic acid) chemically grafted to the surface of a polypropylene fi lm. The plasmonic absorption and the SERS activity of the substrates were studied as a function of the thickness of the grafted layer for a fixed time of nanoparticle synthesis. The results indicate dense three-dimensional packing of plasmonic nanoparticles in the grafted polymer layer. The substrates have a storage-stable and surface-uniform SERS activity.

Selective multi-nanosoldering for fabrication of advanced solution-processed micro/nanoscale metal grid structures

Solution-processed metal grid transparent conductors with low sheet resistance, high optical transmittance and good mechanical flexibility have great potential for use in flexible optoelectronic devices. However, there are still remaining challenges to improve optoelectrical properties and electromechanical stability of the metallic structures due to random loose packings of nanoparticles and the existence of many pores. Here we introduce a selective multi-nanosoldering method to generate robust metallic layers on the thin metal grid structures (< a thickness of 200 nm), which are generated via self-pining assisted direct inking of silver ions. The selective multi-nanosoldering leads to lowering the sheet resistance of the metal grid transparent conductors, while keeping the optical transmittance constant. Also, it reinforces the electromechanical stability of flexible metal grid transparent conductors against a small bending radius or a repeated loading. Finally, organic light-emitting diodes based on the flexible metal grid transparent conductors are demonstrated. Our approach can open a new route to enhance the functionality of metallic structures fabricated using a variety of solution-processed metal patterning methods for next-generation optoelectronic and micro/nanoelectronic applications.

Ruthenium-Loaded Halloysite Nanotubes as Mesocatalysts for Fischer-Tropsch Synthesis.

Halloysite aluminosilicate nanotubes loaded with ruthenium particles were used as reactors for Fischer–Tropsch synthesis. To load ruthenium inside clay, selective modification of the external surface with ethylenediaminetetraacetic acid, urea, or acetone azine was performed. Reduction of materials in a flow of hydrogen at 400 °C resulted in catalysts loaded with 2 wt.% of 3.5 nm Ru particles, densely packed inside the tubes. Catalysts were characterized by N2-adsorption, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray fluorescence, and X-ray diffraction analysis. We concluded that the total acidity and specific morphology of reactors were the major factors influencing activity and selectivity toward CH4, C2–4, and C5+ hydrocarbons in the Fischer–Tropsch process. Use of ethylenediaminetetraacetic acid for ruthenium binding gave a methanation catalyst with ca. 50% selectivity to methane and C2–4. Urea-modified halloysite resulted in the Ru-nanoreactors with high selectivity to valuable C5+ hydrocarbons containing few olefins and a high number of heavy fractions (α = 0.87). Modification with acetone azine gave the slightly higher CO conversion rate close to 19% and highest selectivity in C5+ products. Using a halloysite tube with a 10–20-nm lumen decreased the diffusion limitation and helped to produce high-molecular-weight hydrocarbons. The extremely small C2–C4 fraction obtained from the urea- and azine-modified sample was not reachable for non-templated Ru-nanoparticles. Dense packing of Ru nanoparticles increased the contact time of olefins and their reabsorption, producing higher amounts of C5+ hydrocarbons. Loading of Ru inside the nanoclay increased the particle stability and prevented their aggregation under reaction conditions.

Origin of Mechanical Enhancement in Polymer Nanoparticle (NP) Composites with Ultrahigh NP Loading

Polymer nanoparticle composites (PNC) with ultra high loading of nanoparticles (> 50%) have been shown to exhibit markedly improved strength, stiffness, and toughness simultaneously compared to the neat systems of their components. Recent experimental studies on the effect of polymer fill fraction in these highly loaded PNCs reveal that even at low polymer fill fractions, hardness and modulus increase significantly. In this work, we aim to understand the origin of these performance enhancements by examining the dynamics of both polymer and nanoparticles (NP) under tensile deformation. We perform molecular dynamics (MD) simulations of coarse-grained, glassy polymer in random-close-packed nanoparticle packings with a varying polymer fill fraction. We characterize the mechanical properties of the PNC systems, compare the NP rearrangement behavior, and study the polymer segmental and chain-level dynamics during deformation below the polymer glass transition. Our simulation results confirm the experimentally-observed increase in modulus at low polymer fill fractions, and we provide evidence that the source of mechanical enhancement is the polymer bridging effect.

Hydrothermal SiO2 Nanopowders: Obtaining Them and Their Characteristics.

The technological mode of obtaining amorphous SiO2 nanopowders based on hydrothermal solutions is proposed in this study. Polycondensation of orthosilicic acid as well as ultrafiltration membrane separation, and cryochemical vacuum sublimation were used. The characteristics of nanopowders were determined by tunneling electron microscopy, low-temperature nitrogen adsorption, X-ray diffraction, and small-angle X-ray scattering. The scheme allows to adjust density, particle diameters of nanopowders, specific surface area, as well as diameters, area and volume of the pore. Thus, the structure of nanopowders is regulated—the volume fraction of the packing of spherical particles in aggregates and agglomerates, the size of agglomerates, and the number of particles in agglomerates. The pour densities of the nanopowders depend on the SiO2 content in sols, which were 0.02 to 0.3 g/cm3. Nanoparticles specific surface area was brought to 500 m2/g by low temperature polycondensation. Nanoparticle aggregates specific pore volume (0.2–0.3 g/cm3) weakly depend on powders density. The volume fraction of the packing of SiO2 nanoparticles in aggregates was 0.6–0.7. Solid samples of compacted nanopowders had a compressive strength of up to 337 MPa. Possible applications of hydrothermal SiO2 nanopowders are considered.

Controllable synthesis of silica nanoparticle size and packing efficiency onto PVP‐functionalized PMMA via a sol–gel method

ABSTRACTThis study aimed to investigate synthesis and adsorption behavior of silica nanoparticles onto polyvinylpyrrolidone (PVP)‐functionalized poly(methyl methacrylate) under various conditions such as methanol/water ratio, ammonium hydroxide concentration, polymer contents, tetraethylorthosilicate contents, and total volume of solvent via sol–gel method. First, the copolymerization of methyl acrylate as a comonomer and 1‐dodecanethiol as a chain transfer agent increased the thermal stability of the product; however, the uniformity of the PMMA particles decreased because of the chain transfer reaction. Second, the adsorption behavior and size of silica nanoparticles could be controlled by adjusting the silica synthesis conditions. The adsorbed silica particle size was greatly influenced by the ammonium hydroxide concentration and the addition of water further enhanced the size increase. However, increasing the water content reduced the packing efficiency of the adsorbed silica particles. Increasing the PVP‐functionalized PMMA content at a fixed TEOS content linearly decreased the silica particle size. But TEOS concentration did not significantly affect the silica particle size. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 662–672

Thermal Transport in Nanoparticle Packings Under Laser Irradiation

Abstract Nanoparticle heating due to laser irradiation is of great interest in electronic, aerospace, and biomedical applications. This paper presents a coupled electromagnetic-heat transfer model to predict the temperature distribution of multilayer copper nanoparticle packings on a glass substrate. It is shown that heat transfer within the nanoparticle packing is dominated by the interfacial thermal conductance between particles when the interfacial thermal conductance constant, GIC, is greater than 20 MW/m2K, but that for lower GIC values, thermal conduction through the air around the nanoparticles can also play a role in the overall heat transfer within the nanoparticle system. The coupled model is used to simulate heat transfer in a copper nanoparticle packing used in a typical microscale selective laser sintering (μ-SLS) process with an experimentally measured particle size distribution and layer thickness. The simulations predict that the nanoparticles will reach a temperature of 730 ± 3 K for a laser irradiation of 2.6 kW/cm2 and 1304 ± 23 K for a laser irradiation of 6 kW/cm2. These results are in good agreement with the experimentally observed laser-induced sintering and melting thresholds for copper nanoparticle packing on glass substrates.

Enhancing the adhesion strength of polyurethane coatings by dispersing layered silicates via sonication and high-shear mixing method

Low adhesion strength of polyurethane coating to a steel substrate is often attributed to poor steel preparation. However, the ratio of diisocyanate/polyol and dispersion of fillers within a polyurethane coating matrix influence the adhesion strength, optical and corrosion resistance properties. Poor dispersion of nano-fillers in a polymer coating matrix can lead to low adhesion strength, because close packing of nanoparticles often hides the hydroxyl groups required to form polar–polar bonds with the steel surface. This study combines sonication and high-shear mixing methods with shorter mixing times to prepare polyurethane nanocomposite coatings with various clay concentrations while keeping the ratio of diisocyanate/polyol constant. Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray diffraction, thermogravimetric analysis and pull-off are used to characterize polyurethane nanocomposite coatings. FTIR results confirm that sonication and high-shear mixing successfully prepare polyurethane-based coatings. TEM shows uniformly dispersed clay particles in polyurethane matrices. The adhesion strength improved on addition of 1–5 wt% C30B organoclay, with the highest improvement (34.4%) at 3 wt% loading. The corrosion resistance of polyurethane coatings was improved by the incorporation of organoclays into their matrices. Onset degradation temperature is also delayed by 4.1–8.5% as the clay concentration increased from 1 to 5 wt%.

Effect of polymer–nanoparticle interactions on solvent-driven infiltration of polymer (SIP) into nanoparticle packings: a molecular dynamics study

Dynamics of polymer motion into solvent-filled interstices of nanoparticle packings can be controlled by tuning the polymer–nanoparticle interactions, whose effect on the rate of infiltration is non-monotonic as shown by MD simulations.

Polymer-guided assembly of inorganic nanoparticles.

The self-assembly of inorganic nanoparticles is of great importance in realizing their enormous potentials for broad applications due to the advanced collective properties of nanoparticle ensembles. Various molecular ligands (e.g., small molecules, DNAs, proteins, and polymers) have been used to assist the organization of inorganic nanoparticles into functional structures at different hierarchical levels. Among others, polymers are particularly attractive for use in nanoparticle assembly, because of the complex architectures and rich functionalities of assembled structures enabled by polymers. Polymer-guided assembly of nanoparticles has emerged as a powerful route to fabricate functional materials with desired mechanical, optical, electronic or magnetic properties for a broad range of applications such as sensing, nanomedicine, catalysis, energy storage/conversion, data storage, electronics and photonics. In this review article, we summarize recent advances in the polymer-guided self-assembly of inorganic nanoparticles in both bulk thin films and solution, with an emphasis on the role of polymers in the assembly process and functions of resulting nanostructures. Precise control over the location/arrangement, interparticle interaction, and packing of inorganic nanoparticles at various scales are highlighted.

The influence of gold nanoparticles on the thermal conductivity of water solutions of graphen

The objects of study were water dispersions of raw graphene (hereinafter referred to as graphene-n), higher degree of purification of graphene samples (hereinafter graphene), and nanoparticles of graphene-Au nanoparticles based on them.&#x0D; The thermal conductivity of water graphene dispersions and water dispersions of gold graphene nanoparticles nanostructures at different temperatures and component ratios was investigated. The values ​​of effective thermal conductivity of dry nanofillers are calculated. The temperature dependences of the thermal conductivity of the nanofillers were obtained. It is found that the in-thermal conductivity of water dispersions of purified graphene is higher than the thermal conductivity of raw graphene as a result of better packing of nanoparticles in pure graphene nanofillers compared to raw. The effect of enhancement of thermal conductivity of gold nanoparticles, which is accompanied by higher absolute values of thermal conductivity of nanoparticles of graphene-nanoparticles of gold than the corresponding graphene, was revealed. At the same time, there is a significant difference in thermal conductivity between nanoparticles of graphene nanoparticles of gold.&#x0D; It is established that higher values of thermal conductivity of graphene-nanoparticles nanostructures of gold are the result of the reinforcing action of a gold nanoparticle substrate, which is formed as a result of joint sedimentation with graphene during the formation of nano-flakes from water solution during evaporation of water.

Elimination of Extreme Boundary Scattering via Polymer Thermal Bridging in Silica Nanoparticle Packings: Implications for Thermal Management

Recent advances in our understanding of thermal transport in nanocrystalline systems are responsible for the integration of many technologies into advanced energy systems, including thermoelectric refrigeration systems and renewable energy platforms. However, there is little understanding of heat energy transport mechanisms that govern the thermal properties of disordered nanocomposites. In this work, we explore thermal transport mechanisms in disordered packings of amorphous nanoparticles with and without a polymer filling the interstices in order to quantify the impact of thermal boundary scattering introduced at nanoparticle edges in an already amorphous system and within the context of a minimum thermal conductivity approximation. By fitting a modified minimum thermal conductivity model to temperature-dependent measurements of thermal conductivity from 80 to 300 K, we find that the interstitial polymer eliminates boundary scattering in the disordered nanoparticle packing, which surprisingly leads to a...

Rapid preparation of paper-based plasmonic platforms for SERS applications

A simple spray method is utilized to prepare plasmonic paper loaded with gold nanoparticles (AuNPs) to serve as a signal enhancing substrate for surface enhanced Raman scattering (SERS) spectroscopy. The spray coating of plasmonic AuNPs onto hydrophilic porous paper-based materials notably improves their loading efficiency and distribution profile in much shorter time compare to typical dip- or drop-coating methods. This preparation approach involves the rapid drying of the solution to prevent the loss of the nanoparticles on the hydrophilic paper, which results in the improved packing of the plasmonic nanoparticles with local aggregations. Upon treating these spray-coated substrates with Raman reporter molecules, their sensing capability of SERS is a minimum of 2 times higher than that found with a dip-coated platform. Subsequently applying an additional layer of AuNPs onto these two substrates by dip- and spray-coating methods readily leads to greatly enhanced SERS signals over 2–5 times that are mainly caused by the plasmonic couplings and hot spots of sandwich-type structures. Without the modification of the paper substrates, the way the sandwich structure is formed on the paper materials with typical AuNPs significantly influences the packing and structural properties of the plasmonic nanoparticles, thereby highly impacting the SERS enhancement patterns.

(Invited) Template Free Method for Macroporous SnO2 Thin Film Sensors

Transition metal oxides are attractive candidates for gas sensing thanks to their interesting semiconductive properties [1,2]. In particular, tin oxide (SnO2) is the most utilized n-type metal oxide semiconductor, as it typically provides high sensitivity to a large variety of gas analytes. In this study, we are using the versatility of solution-based approaches to prepare MOS materials at the nanoscale and to control critical film morphology parameters for gas sensing such as crystallinity, grain size, film thickness, as well as surface area (through porosity) – the focus of this paper. In the literature, methods of preparing porous SnO2 have been reported many times. However, they are either i) simple but yield SnO2 with small, hard to access pores (sol-gel), potentially non-contiguous films (nanoparticles packing), or ii) they are more complex and in turn more costly (use of porogen, electrochemical processes etc.). Here, we report on a simple, template-free, one-step process that, if deposited in the right conditions, inherently yields highly porous films with large pores (Fig. 1b). The morphology of the macropores was unanticipated with the pores being self-organized, and completely open to the surface. An important parameter to obtain these pores is to deposit the solution at an optimal aging time, as illustrated in Figure 1. Additionally, other factors such as solution concentration and pH, or the nature of the solvent can also impact the macropores formation. The role played by these factors will be discussed, and hypotheses on the macropores formation mechanism will be proposed. The presence of these macropores led to a two-fold increase in sensitivity in our gas sensing measurements (Fig. 1e, 1f) [3]. Altogether, these results suggest that solution-based processes are very powerful to prepare highly sensitive metal oxide gas sensors. The unique morphologies achieved could be highly advantageous in the context of an electronic nose. References K. Lionti et.al., TechConnect Briefs 2017, Chap. 7, p.219A. Fasoli et.al., IEEE International Symposium on Olfaction and Electronic Nose 2017, p.978K. Lionti et al., 2017, US10020199B1. Figure 1

Ordering, flexibility and frustration in arrays of porphyrin nanorings

The regular packing of atoms, molecules and nanoparticles provides the basis for the understanding of structural order within condensed phases of matter. Typically the constituent particles are considered to be rigid with a fixed shape. Here we show, through a combined experimental and numerical study of the adsorption of cyclic porphyrin polymers, nanorings, on a graphite surface, that flexible molecules can exhibit a rich and complex packing behaviour. Depending on the number of porphyrin sub-units within the nanoring we observe either a highly ordered hexagonal phase or frustrated packing driven by directional interactions which for some arrangements is combined with the internal deformation of the cyclic polymer. Frustration and deformation occur in arrays of polymers with ten sub-units since close packing and co-alignment of neighbouring groups cannot be simultaneously realised for nanorings with this internal symmetry.

Structure Inheritance in Nanoparticle Ink Direct-Writing Processes and Crack-Free Nano-Copper Interconnects Printed by a Single-Run Approach.

When nanoparticle conductive ink is used for printing interconnects, cracks and pores are common defects that deteriorate the electrical conductivity of the printed circuits. Influences of the ink solvent, the solid fraction of the ink, the pre-printing treatment and the sintering parameters on the interconnect morphology and conductivity were investigated. It was found that the impacts of all these factors coupled with each other throughout the whole procedure, from the pre-printing to the post-printing processes, and led to a structure inheritance effect. An optimum process route was developed for producing crack-free interconnects by a single-run direct-writing approach using home-made nano-copper ink. A weak gel was promoted in the ink before printing in the presence of long-chain polymers and bridging molecules by mechanical agitation. The fully developed gel network prevented the phase separation during ink extrusion and crack formations during drying. With the reducing agents in the ink and slow evaporation of the ink solvent, compact packing and neck joining of copper nanoparticles were obtained after a two-step sintering process. The crack-free interconnects successfully produced have a surface roughness smaller than 1.5 μm and the square resistances as low as 0.01 Ω/□.

Template growth of Au/Ag nanocomposites on phosphorene for sensitive SERS detection of pesticides

We report template growth and dense packing of noble metallic nanoparticles (NPs) on few-layer phosphorene for sensitive surface-enhanced Raman scattering (SERS) detection. Phosphorene obtained by electrochemical exfoliation serves as both the template and reductant in the fabrication of noble metallic NPs which are dispersed on phosphorene without aggregation or pile-up. The BP/Ag/Au and BP/Au/Ag nanocomposites with a nanogap structure exhibit excellent SERS sensitivity and reproducibility with respect to Rhodamine 6G. The BP/Au/Ag nanocomposite is further utilized as the SERS substrate for the detection of two fungicides, thiabendazole and thiram, and detection limits of 10–7 and 10–8 M are achieved. Template growth of Au/Ag nanocomposites is demonstrated to be a green strategy for the fabrication of SERS substrates and has large potential in applications such as pesticide detection.

Effect of particle size distribution on near-field thermal energy transfer within the nanoparticle packings

Nanoscale size effects give rise to near-field thermal considerations when heating nanoparticles under high laser power. We solve Maxwell’s equations in the frequency domain to analyze near-field thermal energy effects for three nanoparticle assemblies with different variances in particle sizes and show that heat dissipation generally decreases as the spread in nanoparticle sizes increases within the nanoparticle packing. For this study, log-normally distributed copper nanoparticle packings with a mean radius of 116 nm and three different standard deviations (12, 48, and 84 nm) were created by using a discrete element model in which a specified number of particles is generated. The nanoparticle packings in the simulation are created by randomly placing each nanoparticle into the packing domain with a random initial velocity and a position. The nanoparticles are then allowed to interact with each other under gravitational and weak van der Waals forces until they settle to form a stable packing configuration. A finite-difference frequency-domain analysis, which yields the electromagnetic field distribution, is then applied to the packing by solving Maxwell’s equations to obtain absorption, scattering, and extinction coefficients. This analysis is used to calculate the surface plasmon effects due to the electromagnetic coupling between the nanoparticles and the dielectric medium under the different distributions and show that different particle distributions can create different plasmonic effects in the packing domain, which results in nonlocal heat transport. Overall, this analysis helps to reveal how sintering quality can be enhanced by creating stronger laser–particle interactions for specific groups of nanoparticles.

Computer simulation study on the self-assembly of tethered nanoparticles with tunable shapes.

We built a tethered nanoparticle (TNP) model that is composed of a nanoparticle with a hydrophobic tethered polymer chain. The shape of the nanoparticle can be tuned from a pure rigid cube to a soft sphere, mimicking the increase of grafting density on the nanocube surfaces. With this model, we study the self-assembly of TNPs in dilute solution using a dissipative particle dynamics simulation technique, and especially focus on the influence of particle shape, tethered chain length, and grafting density on the self-assembly structures. Some intriguing aggregates such as spherical micelles, pearl-necklace-like structures, cubic columnar structures, handshake structures, core–shell–corona micelles, and four-patch micelles have been observed when varying the interactions between cubes and solvents and the lengths of tethered chain. Modifying the nanocube surface with some hydrophilic grafted chains helps the TNPs form small micelles. Increased steric repulsion due to chain overlapping at larger grafting densities results in shape transformation of the nanoparticle from a rigid cube to a soft sphere. In these cases, the self-assembled structures are characterized by the packing of nanoparticles on the micelle surface, and the typical packing mode turns from rectangular (typical for cubes) to hexagonal (typical for spheres).

Patterning polymer-filled nanoparticle films via leaching-enabled capillary rise infiltration (LeCaRI)

Leaching-enabled capillary rise infiltration is a versatile method to pattern polymer-filled nanoparticle films by leaching mobile species from an elastomer network into nanoparticle packings.