Carola Esposito Corcione

Characterization of Nanocomposites by Thermal Analysis

In materials research, the development of polymer nanocomposites (PN) is rapidly emerging as a multidisciplinary research field with results that could broaden the applications of polymers to many different industries. PN are polymer matrices (thermoplastics, thermosets or elastomers) that have been reinforced with small quantities of nano-sized particles, preferably characterized by high aspect ratios, such as layered silicates and carbon nanotubes. Thermal analysis (TA) is a useful tool to investigate a wide variety of properties of polymers and it can be also applied to PN in order to gain further insight into their structure. This review illustrates the versatile applications of TA methods in the emerging field of polymer nanomaterial research, presenting some examples of applications of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical thermal analysis (DMTA) and thermal mechanical analysis (TMA) for the characterization of nanocomposite materials.

Free form fabrication of silica moulds for aluminium casting by stereolithography

Purpose – In this work, the production of ceramic moulds for aluminium casting using a stereolithographic apparatus (SLA) is presented.Design/methodology/approach – Suspensions of silica powders in a photoreactive resin were used in a standard SLA equipment in order to build green parts. SLA, SLA‐250 (3D System, Valencia, CA) was modified in order to fabricate a ceramic green parts.Findings – A characterization of mechanical properties of the material samples was performed. Finally, moulds for aluminium casting were obtained either using the stereolithographic part as a green mould, either by pyrolisis of the organic binder and subsequent sintering at high temperature.Research limitations/implications – Future investigations will be devoted to optimise the process and the mechanical performances of the sintered parts, improving the rheological properties of suspensions and reducing the building time.Originality/value – This is a novel work on the production of ceramic moulds for aluminium casting using a SLA.

Microgel Modified UV-Cured Methacrylic-Silica Hybrid: Synthesis and Characterization

An innovative photopolymerizable microgel modified UV-cured acrylic-silica hybrid formulation was developed and characterized for possible use as protective coating for different substrates. A deep investigation, aiming at providing a strong scientific basis for the production of organic-inorganic (O-I) hybrids exhibiting phase co-continuity, was firstly carried out. The O-I hybrid first proposed in this study was obtained from organic precursors with a high siloxane content, which are mixed with tetraethoxysilane (TEOS) in such a way to produce co-continuous silica nanodomains dispersed within the crosslinked organic phase, as a result of the sol-gel process. The first part of the research deals with the selection and optimization of suitable systems through appropriate chemical modifications, in order to ensure that curing reactions can be carried out at room temperature and in the presence of UV radiation. Firstly, the silica domains are formed, followed by crosslinking reactions of the acrylic groups in the oligomer via a free radical polymerization. The crosslinking reaction was controlled with the use of a suitable photoinitiator. Most of the experimental work was devoted to understanding the morphology of the hybrid system, both in uncured and cured states, and to assess its final thermal and optical properties, using different experiential techniques.

Cold-Curing Structural Epoxy Resins: Analysis of the Curing Reaction as a Function of Curing Time and Thickness

The curing reaction of a commercial cold-curing structural epoxy resin, specifically formulated for civil engineering applications, was analyzed by thermal analysis as a function of the curing time and the sample thickness. Original and remarkable results regarding the effects of curing time on the glass transition temperature and on the residual heat of reaction of the cold-cured epoxy were obtained. The influence of the sample thickness on the curing reaction of the cold-cured resin was also deeply investigated. A highly exothermal reaction, based on a self-activated frontal polymerization reaction, was supposed and verified trough a suitable temperature signal acquisition system, specifically realized for this measurement. This is one of the first studies carried out on the curing behavior of these peculiar cold-cured epoxy resins as a function of curing time and thickness.

Development and characterization of novel photopolymerizable formulations for stereolithography

Abstract Novel photopolymerizable formulations, able to photopolymerize with a dual mechanism (cationic and radical), were developed and characterized as potential resins for stereolithography (SL) process. The influence of the presence of organically modified boehmite nanoparticles on the properties of the photopolymerizable mixtures was also analyzed. The main properties required for a liquid SL resin are a high reactivity and a low viscosity. All of the experimental formulations produced, even in the presence of boehmite nanoparticles, are able to satisfy these significant requirements. Physical-mechanical and thermal properties of the photocured samples, obtained starting from the experimental formulations, were finally measured. The cured nanocomposite bars show a high transparency, confirming the good dispersion of the nanofiller in the polymeric matrix and possess improved glass transition temperature (Tg) and mechanical performances, compared to the unfilled system and to a commercial stereolithographic resin. These results suggest the possibility of using the novel nanofilled photopolymerizable suspensions in the stereolithographic apparatus to build, not only esthetical, but also functional prototypes.

UV Reduced Graphene Oxide PEDOT:PSS Nanocomposite for Perovskite Solar Cells

In this paper, we have investigated the possibility to realize a nanocomposite buffer layer for perovskite solar cells, based on polyelectrolyte poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) PEDOT:PSS and graphene oxide (GO). To this aim, GO, prepared by a modified Hummers method, was mixed with PEDOT:PSS by solvent swelling method and reduced in situ into the polymer matrix through a green and simple method, by using UV radiation. Thin nanocomposite layers were spin coated on different substrates and characterized by several techniques. GO reduction was first analyzed by XPS analyses, monitoring the decrease of the intensity of the peak of the oxygen groups linked to carbon. The grade of the dispersion of GO into PEDOT:PSS was also analyzed by scanning electron microscopy. Sheet resistance measurements of the films with and without GO before and after UV treatment was performed. The thermal stability of the nanocomposites was then evaluated by thermogravimetric analyses. The nanocomposite layer was finally employed in a perovskite solar cell to evaluate the effect of GO reduction on power conversion efficiency. The interface interaction between the nanocomposite and the perovskite precursors was analyzed by contact angle measurements.

Cure kinetics and physical characterization of epoxy/modified boehmite nanocomposites

Abstract Nanocomposites based on a cross-linked epoxy matrix with the addition of a reinforcing organically modified boehmite nano-phase were realized and characterized with the aim to produce systems possessing enhanced properties over commercial epoxy systems. Different amounts of a commercially available organically modified boehmite were added to a diglycidyl ether of bisphenol A (DGEBA) epoxy matrix. The rheological characteristic and kinetic behavior of the liquid nano-filled mixtures were analyzed and compared to those displayed by the un-filled resin. A mathematical model was applied to the experimental rheological data in order to assess the aspect ratio of the nano-filler. A proper equation was employed to model the cure kinetics of the nano-filled epoxy systems. The nanocomposites were heat-cured in the presence of an aromatic amine hardener. They were, then, characterized by scanning electron microscopy with EDS analysis, dynamic mechanical thermal analysis, differential scanning calorimetry, and Flexural and Hardness tests. Significant increase in the glass transition temperature, Shore D hardness and maximum flexural strength was found. The experimental results demonstrated the effectiveness of the o-boehmite nano-filler to improve the physical and mechanical properties of the epoxy resin. Further studies are in progress to verify the protective efficiency of the epoxy-boehmite nanocomposite when applied on different substrates as adhesive or coating for construction materials, such as porous stones, concrete, wood, and metal.

GO/PEDOT:PSS nanocomposites: effect of different dispersing agents on rheological, thermal, wettability and electrochemical properties

In this work glucose (G), α-cyclodextrin (α-CD) and sodium salt of carboxymethyl cellulose (CMCNa) are used as dispersing agents for graphene oxide (GO), exploring the influence of both saccharide units and geometric/steric hindrance on the rheological, thermal, wettability and electrochemical properties of a GO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) nanocomposite. By acting on the saccharide-based additives, we can modulate the rheological, thermal, and wettability properties of the GO/PEDOT:PSS nanocomposite. Firstly, the influence of all the additives on the rheological behaviour of GO and PEDOT:PSS was investigated separately in order to understand the effect of the dispersing agent on both the components of the ternary nanocomposite, individually. Subsequently, steady shear and dynamic frequency tests were conducted on all the nanocomposite solutions, characterized by thermal, wettability and morphological analysis. Finally, the electrochemical properties of the GO/PEDOT composites with different dispersing agents for supercapacitors were investigated using cyclic voltammetry (CV). The CV results revealed that GO/PEDOT with glucose exhibited the highest specific capacitance among the systems investigated.

3D printing of hydroxyapatite polymer-based composites for bone tissue engineering

Abstract Skeletal defects reconstruction, using custom-made substitutes, represents a valid solution to replacing lost and damaged anatomical bone structures, renew their original function, and at the same time, restore the original aesthetic aspect. Rapid prototyping (RP) techniques allow the construction of complex physical models based on 3D clinical images. However, RP machines usually work with synthetic polymers; therefore, producing custom-made scaffolds using a biocompatible material directly by RP is an exciting challenge. The aim of the present work is to investigate the potentiality of 3D printing as a manufacturing method to produce an osteogenic hydroxyapatite-polylactic acid bone graft substitute.

Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins

This article compares the catalytic activities of oxidized carbon black (oCB) and graphene oxide (eGO) samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA) with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC). Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m2/g), as oxidized by the Hummers’ method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide.