The regulation of engineered nanoparticles requires a widely agreed definition of such particles. Nanoparticles are routinely defined as particles with sizes between about 1 and 100 nm that show properties that are not found in bulk samples of the same material. Here we argue that evidence for novel size-dependent properties alone, rather than particle size, should be the primary criterion in any definition of nanoparticles when making decisions about their regulation for environmental, health and safety reasons. We review the size-dependent properties of a variety of inorganic nanoparticles and find that particles larger than about 30 nm do not in general show properties that would require regulatory scrutiny beyond that required for their bulk counterparts.

/pdf/towards-a-definition-of-inorganic-nanoparticles-from-an-4qpaj5a6q5.pdf

Towards a definition of inorganic nanoparticles from an environmental, health and safety perspective

The structural properties of free nanoclusters are reviewed. Special attention is paid to the interplay of energetic, thermodynamic, and kinetic factors in the explanation of cluster structures that are actually observed in experiments. The review starts with a brief summary of the experimental methods for the production of free nanoclusters and then considers theoretical and simulation issues, always discussed in close connection with the experimental results. The energetic properties are treated first, along with methods for modeling elementary constituent interactions and for global optimization on the cluster potential-energy surface. After that, a section on cluster thermodynamics follows. The discussion includes the analysis of solid-solid structural transitions and of melting, with its size dependence. The last section is devoted to the growth kinetics of free nanoclusters and treats the growth of isolated clusters and their coalescence. Several specific systems are analyzed.

/pdf/structural-properties-of-nanoclusters-energetic-56vj4t3ucw.pdf

Structural properties of nanoclusters: Energetic, thermodynamic, and kinetic effects

In this article, the effects of size and confinement at the nanometre size scale on both the melting temperature, Tm, and the glass transition temperature, Tg, are reviewed. Although there is an accepted thermodynamic model (the Gibbs–Thomson equation) for explaining the shift in the first-order transition, Tm, for confined materials, the depression of the melting point is still not fully understood and clearly requires further investigation. However, the main thrust of the work is a review of the field of confinement and size effects on the glass transition temperature. We present in detail the dynamic, thermodynamic and pseudo-thermodynamic measurements reported for the glass transition in confined geometries for both small molecules confined in nanopores and for ultrathin polymer films. We survey the observations that show that the glass transition temperature decreases, increases, remains the same or even disappears depending upon details of the experimental (or molecular simulation) conditions. Indeed, different behaviours have been observed for the same material depending on the experimental methods used. It seems that the existing theories of Tg are unable to explain the range of behaviours seen at the nanometre size scale, in part because the glass transition phenomenon itself is not fully understood. Importantly, here we conclude that the vast majority of the experiments have been carried out carefully and the results are reproducible. What is currently lacking appears to be an overall view, which accounts for the range of observations. The field seems to be experimentally and empirically driven rather than responding to major theoretical developments.

https://iopscience.iop.org/article/10.1088/0953-8984/17/15/R01/pdf

Effects of confinement on material behaviour at the nanometre size scale

Size dependence of nanostructures: Impact of bond order deficiency

Tin–lead solder alloys are widely used in the electronic industry. They serve as interconnects that provide the conductive path required to achieve connection from one circuit element to another. There are increasing concerns with the use of tin–lead alloy solders in recognition of hazards of using lead. Lead-free solders and electrically conductive adhesives (ECAs) have been considered as the most promising alternatives of tin-lead solder. ECAs consist of a polymeric resin (such as, an epoxy, a silicone, or a polyimide) that provides physical and mechanical properties such as adhesion, mechanical strength, impact strength, and a metal filler (such as, silver, gold, nickel or copper) that conducts electricity. ECAs offer numerous advantages over conventional solder technology, such as environmental friendliness, mild processing conditions (enabling the use of heat-sensitive and low-cost components and substrates), fewer processing steps (reducing processing cost), low stress on the substrates, and fine pitch interconnect capability (enabling the miniaturization of electronic devices). Therefore, conductive adhesives have been used in liquid crystal display (LCD) and smart card applications as an interconnect material and in flip–chip assembly, chip scale package (CSP) and ball grid array (BGA) applications in replacement of solder. However, no currently commercialized ECAs can replace tin–lead metal solders in all applications due to some challenging issues such as lower electrical conductivity, conductivity fatigue (decreased conductivity at elevated temperature and humidity aging or normal use condition) in reliability testing, limited current-carrying capability, and poor impact strength. Considerable research has been conducted recently to study and optimize the performance of ECAs, such as electrical, mechanical and thermal behaviors improvement as well as reliability enhancement under various conditions. This review article will discuss the materials, applications and recent advances of electrically conductive adhesives as an environmental friendly solder replacement in the electronic packaging industry.

Recent advances of conductive adhesives as a lead-free alternative in electronic packaging: Materials, processing, reliability and applications

The melting behavior of 0.1\char21{}10-nm-thick discontinuous indium films formed by evaporation on amorphous silicon nitride is investigated by an ultrasensitive thin-film scanning calorimetry technique. The films consist of ensembles of nanostructures for which the size dependence of the melting temperature and latent heat of fusion are determined. The relationship between the nanostructure radius and the corresponding melting point and latent heat is deduced solely from experimental results (i.e., with no assumed model) by comparing the calorimetric measurements to the particle size distributions obtained by transmission electron microscopy. It is shown that the melting point of the investigated indium nanostructures decreases as much as 110 K for particles with a radius of 2 nm. The experimental results are discussed in terms of existing melting point depression models. Excellent agreement with the homogeneous melting model is observed.

/pdf/size-dependent-melting-point-depression-of-nanostructures-j7yev84lq0.pdf

Size-dependent melting point depression of nanostructures: Nanocalorimetric measurements

We report a study of the thermodynamic properties of indium clusters on a $\mathrm{SiN}{}_{x}$ surface during the early stages of thin film growth using a sensitive nanocalorimetry technique. The measurements reveal the presence of abnormal discontinuities in the heat of melting below $100\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$. These discontinuities, for which temperature separation corresponds to a spatial periodicity equal to the thickness of an indium monolayer, are found to be related to the atomic ``magic numbers,'' i.e., the number of atoms necessary to form a complete shell of atoms at particle surface.

/pdf/discrete-periodic-melting-point-observations-for-1sey6rp7nx.pdf

Discrete periodic melting point observations for nanostructure ensembles

We introduce a scanning calorimeter for use with a single solid or liquid sample with a volume down to a few nanoliters. Its use is demonstrated with the melting of 52 nL of indium, using heating rates from 100 to 1000 K/s. The heat of fusion was measured to within 5% of the bulk value, and the sensitivity of the measurement was ±7 μW. The heat of vaporization of water was measured in the scanning mode to be within ±23% of the bulk value by actively vaporizing water droplets from 2 to 100 nL in volume. Results within 25% were obtained for the heat of vaporization by using the calorimeter in a heat-conductive mode and measuring the passive evaporation of water. Temperature measurements over a period of 10 h had a standard deviation of 3 mK.

/pdf/scanning-calorimeter-for-nanoliter-scale-liquid-samples-jn87jvfv3e.pdf

Scanning calorimeter for nanoliter-scale liquid samples

We used thin-film differential scanning calorimetry to investigate the melting of isolated polyethylene single crystals with lamellar thicknesses of 12 ± 1 nm. We observed the melting of as few as 25 crystals. Over a wide number of crystals (25-2000 crystals), the heat of fusion was 40% larger than the bulk value. The melting temperature of the isolated single crystals was 123 ± 2 °C, 9 °C lower than that of the bulk material. We also measured the heat of fusion of quenched crystals (±15%) over a wide range of heating rates (20,000-100,000 K/s). Annealing the quenched crystals resulted in shifts in the endotherm peak by as much as 15 °C.

/pdf/nanoscale-calorimetry-of-isolated-polyethylene-single-3hoaeiln2r.pdf

Nanoscale calorimetry of isolated polyethylene single crystals

http://www.clinicalmicrobiologyandinfection.com/article/S1198743X22006103/pdf

A. T. Kwan

Papers

Size-dependent melting point depression of nanostructures: Nanocalorimetric measurements

Discrete periodic melting point observations for nanostructure ensembles

Scanning calorimeter for nanoliter-scale liquid samples

Nanoscale calorimetry of isolated polyethylene single crystals

Antibiotic resistance associated with the COVID-19 pandemic: a systematic review and meta-analysis