Oscillation Dynamics of Dielectric Polymer Droplets during Electrohydrodynamic Jetting in a Wide Range of Viscosities.

The electrohydrodynamic (EHD) jetting of fluids is used for several applications such as inkjet printing, atomization of analyte in mass spectrometry, liquid metal alloy ion sources, and electrospinning of polymer fibers. Historically, the bulk of research has focused on nonviscous, highly conductive fluids which are most suitable for EHD spray and printing, while there is relatively little experimental work on EHD jetting of highly viscous liquid dielectrics. We studied the dynamics of oscillation and pulsating jetting from a suspended drop of polydimethylsiloxane (PDMS) polymers in an electric field, with particular attention to the viscosity dependence of the oscillation period and meniscus elongation and contraction time over a wide viscosity range (102-105 cSt). The reported results could help the appropriate design of EHD processes and may open new possibilities for the rheological characterization of liquid polymers using small volumes at the scale of nanoliters.

Experimental and Numerical Investigation of the Die Swell in 3D Printing Processes.

Fused deposition modelling is one of the most widely used additive manufacturing techniques and the diffusion of 3D printers has increased in popularity even further in recent times. Since high precision is required in 3D printing, a good control over the extrusion process is necessary. In this regard, a crucial phenomenon to be accounted for is the die or extrudate swell, i.e., the enlargement of the cross-section of the strand when coming out of the printer nozzle. While this phenomenon has been studied in large scale extruders, it has not yet been investigated in depth for 3D printing processes. In this work, the die swell phenomenon observed in a printed PLA filament is studied by experiments and fluid dynamic simulations. A novel, easy-to-use, accurate and fast procedure for measuring the value of the die swell ratio during the printing process is developed, accounting for typical errors related to a non-constant strand diameter and possible oscillations of the filament with respect to the extrusion direction. As the printing velocity is increased, a linearly increasing swelling ratio is observed at low printing speeds. The trend flattens at moderate speed values. A sudden increase is found at high printing velocities. The swelling ratio measured with the proposed technique is compared with the results of multi-mode viscoelastic simulations at different temperatures. A fair agreement between the experimental measurements and the numerical predictions is found for printing velocities that are typically employed in commercial 3D printers, supporting the reliability of the developed procedure.

Linking Processing Parameters and Rheology to Optimize Additive Manufacturing of k-Carrageenan Gel Systems.

Additive manufacturing-in particular, three-dimensional (3D) printing-has been introduced since the late 1980s, offering a novel paradigm for engineering design and manufacturing, as it allows the fabrication of very complex structures. Additive manufacturing of hydrogels is a very popular method to produce scaffolds to be used in tissue engineering and other biomedical applications, as well as in other advanced technological areas. When printing a thermoreversible physical hydrogel, a subtle balance between thermal and rheological parameters exists. The characteristic times of the sol-gel transition, regulated by a well-defined thermal history, must be optimized with respect to the characteristic processing times. In this work, we use this thermo-rheological approach to the additive manufacturing of a physical hydrogel. A low-cost desktop 3D printer for thermoplastic polymers was suitably modified to print a 1.5 wt% solution of k-carrageenan. The thermal behavior of the printer was determined by performing experimental measurements of the temperature-time evolution during the different processing steps, from solution loading, to the extrusion of the incoming gel, to the final solidification stage. In parallel, linear viscoelastic oscillatory shear measurements were performed in a rotational rheometer under thermal histories as close as possible to those previously measured in the printing process. The comparison between the rheological results and the quality of printing under different thermal histories is presented and discussed, highlighting the main relations between rheological and processing behavior, which are helpful in the assessment and optimization of the printing conditions.

Microfoamed Strands by 3D Foam Printing.

We report the design, production, and characterization of microfoamed strands by means of a green and sustainable technology that makes use of CO2 to create ad-hoc innovative bubble morphologies. 3D foam-printing technology has been recently developed; thus, the foaming mechanism in the printer nozzle is not yet fully understood and controlled. We study the effects of the operating parameters of the 3D foam-printing process to control and optimize CO2 utilization through a maximization of the foaming efficiency. The strands' mechanical properties were measured as a function of the foam density and explained by means of an innovative model that takes into consideration the polymer's crystallinity content. The innovative microfoamed morphologies were produced using a bio-based and compostable polymer as well as polylactic acid and were then blown with CO2. The results of the extensive experimental campaigns show insightful maps of the bubble size, density, and crystallinity as a function of the process parameters, i.e., the CO2 concentration and temperature. A CO2 content of 15 wt% enables the acquirement of an incredibly low foam density of 40 kg/m3 and porosities from the macro-scale (100-900 µm) to the micro-scale (1-10 µm), depending on the temperature. The foam crystallinity content varied from 5% (using a low concentration of CO2) to 45% (using a high concentration of CO2). Indeed, we determined that the crystallinity content changes linearly with the CO2 concentration. In turn, the foamed strand's elastic modulus is strongly affected by the crystallinity content. Hence, a corrected Egli's equation was proposed to fit the strand mechanical properties as a function of foam density.

An Experimental and Numerical Investigation on Bubble Growth in Polymeric Foams.

The cellular morphology of thermoplastic polymeric foams is a key factor for their performances. Three possible foam morphologies exist, namely, with closed cells, interconnected cellular structure, and open cells. In the gas foaming technology, a physical blowing agent, e.g., CO2 or N2, is used to form bubbles at high pressure in softened/melted polymers. As a consequence of a pressure quench, the bubbles grow in the liquid matrix until they impinge and possibly break the thin liquid films among them. If film breakage happens, the broken film may retract due to the elastic energy accumulated by the polymeric liquid during the bubble growth. This, in turn, determines the final morphology of the foam. In this work, we experimentally study the growth of CO2 bubbles in a poly(e-caprolactone) (PCL) matrix under different pressure conditions. In addition, we perform three-dimensional direct numerical simulations to support the experimental findings and rationalize the effects of the process parameters on the elastic energy accumulated in the liquid at the end of the bubble growth, and thus on the expected morphology of the foam. To do that, we also extend the analytic model available in the literature for the growth of a single bubble in a liquid to the case of a liquid with a multi-mode viscoelastic constitutive equation.

Expanded Beads of High Melt Strength Polypropylene Moldable at Low Steam Pressure by Foam Extrusion.

We explore the foam extrusion of expanded polypropylene with a long chain branched random co-polypropylene to make its production process simpler and cheaper. The results show that the presence of long chain branches infer high melt strength and, hence, a wide foamability window. We explored the entire window of foaming conditions (namely, temperature and pressure) by means of an ad-hoc extrusion pilot line design. It is shown that the density of the beads can be varied from 20 to 100 kg/m3 using CO2 and isobutane as a blowing agent. The foamed beads were molded by steam-chest molding using moderate steam pressures of 0.3 to 0.35 MPa independently of the closed cell content. A characterization of the mechanical properties was performed on the molded parts. The steam molding pressure for sintering expanded polypropylene beads with a long chain branched random co-polypropylene is lower than the one usually needed for standard polypropylene beads by extrusion. The energy saving for the sintering makes the entire manufacturing processes cost efficient and can trigger new applications.

Flowering in bursting bubbles with viscoelastic interfaces.

The lifetime of bubbles, from formation to rupture, attracts attention because bubbles are often present in natural and industrial processes, and their geometry, drainage, coarsening, and rupture strongly affect those operations. Bubble rupture happens rapidly, and it may generate a cascade of small droplets or bubbles. Once a hole is nucleated within a bubble, it opens up with a variety of shapes and velocities depending on the liquid properties. A range of bubble rupture modes are reported in literature in which the reduction of a surface energy drives the rupture against inertial and viscous forces. The role of surface viscoelasticity of the liquid film in this colorful scenario is, however, still unknown. We found that the presence of interfacial viscoelasticity has a profound effect in the bubble bursting dynamics. Indeed, we observed different bubble bursting mechanisms upon the transition from viscous-controlled to surface viscoelasticity-controlled rupture. When this transition occurs, a bursting bubble resembling the blooming of a flower is observed. A simple modeling argument is proposed, leading to the prediction of the characteristic length scales and the number and shape of the bubble flower petals, thus paving the way for the control of liquid formulations with surface viscoelasticity as a key ingredient. These findings can have important implications in the study of bubble dynamics, with consequences for the numerous processes involving bubble rupture. Bubble flowering can indeed impact phenomena such as the spreading of nutrients in nature or the life of cells in bioreactors.

Axisymmetric bare freestanding films of highly viscous liquids: Preparation and real-time investigation of capillary leveling.

HYPOTHESIS: Thin liquid films are important in many scientific fields. In particular, films with both the surface layers exposed to a different fluid phase, known as freestanding films, are relevant in the ambit of foams and emulsions. Hence, there is a great interest in developing novel techniques allowing to form large and stable freestanding liquid films and to follow their dynamics. EXPERIMENTS: We develop a novel opto-mechanical tool allowing to perform and study the preparation and the capillary leveling flow of axisymmetric bare freestanding liquid films. The tool is composed by a customized motorized iris diaphragm and by an innovative joint imaging setup combining digital holography and white light color interferometry that enables real-time measurement of film thickness over a large field of view. The dynamics of films made of a model Newtonian fluid, i.e., high-viscosity silicone oil, is studied. Direct numerical simulations and a hydrodynamic model based on the lubrication theory are used to support the experimental results. FINDINGS: Iris opening induces the formation of large circular freestanding films with a stepped profile. Once iris opening is stopped, the films undergo a capillary leveling flow tending to flatten their profile. The leveling flow follows the theoretical scaling given by Ilton et al. [1]. We prove through numerical simulations that an equi-biaxial extensional flow occurs at the film center. Furthermore, we observe the formation and dynamics of dimples in bare freestanding films for the first time.

Modelling Sorption Thermodynamics and Mass Transport of n-Hexane in a Propylene-Ethylene Elastomer.

Optimization of post polymerization processes of polyolefin elastomers (POE) involving solvents is of considerable industrial interest. To this aim, experimental determination and theoretical interpretation of the thermodynamics and mass transport properties of POE-solvent mixtures is relevant. Sorption behavior of n-hexane vapor in a commercial propylene-ethylene elastomer (V8880 VistamaxxTM from ExxonMobil, Machelen, Belgium) is addressed here, determining experimentally the sorption isotherms at temperatures ranging from 115 to 140 °C and pressure values of n-hexane vapor up to 1 atm. Sorption isotherms have been interpreted using a Non Random Lattice Fluid (NRLF) Equation of State model retrieving, from data fitting, the value of the binary interaction parameter for the n-hexane/V8880 system. Both the cases of temperature-independent and of temperature-dependent binary interaction parameter have been considered. Sorption kinetics was also investigated at different pressures and has been interpreted using a Fick's model determining values of the mutual diffusivity as a function of temperature and of n-hexane/V8880 mixture composition. From these values, n-hexane intra-diffusion coefficient has been calculated interpreting its dependence on mixture concentration and temperature by a semi-empiric model based on free volume arguments.

[Validation of surgical masks during COVID19 emergency: activities at the University of Napoli Federico II]. / Validazione di maschere chirurgiche nella fase di emergenza COVID19: l'esperienza dell'Università degli Studi di Napoli Federico II.

SUMMARY: During COVID-19 pandemic crisis, Italian Government has approved Law Decree no. 18 of 17 march 2020, in which art. 15 allows enterprises to produce, import and commercialize surgical masks notwithstanding the current rules of product certification. It is just required that the interested enterprises send to the Italian National Institute of Health a selfcertification in which they declare the technical characteristics of the masks and that masks are produced according to the safety requirements. In this context, a technical-scientific unit was established at the University of Napoli Federico II to provide interested enterprises with state-of-the-art consultancy, testing and measurement services, adhering to rigorous scientific protocols. Characterization tests were carried out on 163 surgical masks and/or materials for their construction and they have enabled the identification of pre-screening criteria to simplify the procedure for evaluating surgical masks using methods for assessing the filtration efficiency of particles and aerosols. Based on experimental results, it has been observed that a filtration efficiency for particles with sizes larger that 650 nm (PFE>650) exceeding 35% might guarantees a bacterial filtration efficiency (BFE) higher than 95% while BFE values higher than 98% are obtained when the PFE>650 is larger than 40%. PFE measurement is extremely simpler with respect to BFE, the latter being time-consuming and requiring specific equipment and methods for its realization. Many tested materials have shown the capability to assure high filtration efficiencies but Spundonded-Meltblown-Spunbonded (SMS), that are layers of non-woven fabric with different weights of Meltblown, can simultaneously guarantee high particle filtration efficiencies with pressure drop values (breathability) in the limits to classify the surgical masks as Type II/IIR. In fact, the fabric products analyzed so far have not been able to simultaneously guarantee adequate BFE and breathability values. On the contrary, Spunbonds of adequate weights can virtually verify both requirements and accredit themselves as possible materials for the production of surgical masks, at least of Type I. Further studies are needed to verify the possibility of producing low-cost, reusable surgical masks that could meet the criteria of circular economy.

Elasticity in Bubble Rupture.

When a Newtonian bubble ruptures, the film retraction dynamics is controlled by the interplay of surface, inertial, and viscous forces. In case a viscoelastic liquid is considered, the scenario is enriched by the appearance of a new significant contribution, namely, the elastic force. In this paper, we investigate experimentally the retraction of viscoelastic bubbles inflated at different blowing rates, showing that the amount of elastic energy stored by the liquid film enclosing the bubble depends on the inflation history and in turn affects the velocity of film retraction when the bubble is punctured. Several viscoelastic liquids are considered. We also perform direct numerical simulations to support the experimental findings. Finally, we develop a simple heuristic model able to interpret the physical mechanism underlying the process.

Dynamic fluid-film interferometry as a predictor of bulk foam properties.

Understanding and enabling the control of the properties of foams is important for a variety of commercial processes and consumer products. In these systems, the role of surface active compounds has been the subject of many investigations using a wide range of techniques. The study of their influence on simplified geometries such as two bubbles in a liquid or a thin film of solution (such as in the well-known Scheludko cell), has yielded important fundamental understanding. Similarly, in this work an interferometric technique is used to study the dynamic evolution of the film formed by a single bubble being pressed against a planar air-liquid interface. Here interferometry is used to dynamically measure the total volume of liquid contained within the thin-film region between the bubble and the planar interface. Three different small-molecule, surfactant solutions were investigated and the data obtained via interferometry were compared to measurements of the density of bulk foams of the same solutions. The density measurements were collected with a simple, but novel technique using a conical-shaped bubbling apparatus. The results reveal a strong correlation between the measurements on single bubbles and complete foams. This suggests that further investigations using interferometric techniques can be instrumental to building a more detailed mechanistic understanding of how different surface-active compounds influence foam properties. The results also reveal that the commonly used assumption that surfactant-laden interfaces may be modeled as immobile, is too simplistic to accurately model interfaces with small-molecule surfactants.