Francesco Baldi

Network architecture and shape memory behavior of cold-worked epoxies

The shape memory behavior of polymers derives from a combination of their molecular architecture and thermomechanical history. In this study, several epoxies with various network architectures were prepared using mixtures of a diepoxide resin, a monoepoxide resin, and an aliphatic diamine hardener. A nonconventional cold-working programming, carried out below Tg, was employed to set the materials in a temporary configuration and allowed to fix considerable amounts of the applied strain. The shape memory behavior was evaluated through transient heating and isothermal recovery tests. All the resins are capable of complete recovery, which occurs as a sequence of an early process taking place below Tg and a major one close to Tg, which acted as the switching temperature (Tswitch). The proximity of the deformation temperature to Tg influenced the amount of strain recovered within each process. It was shown that resins with different structures, although presenting similar Tswitch, may have different recovery kinetics, and the roles of the network density and the chain stiffness on the recovery rate were evidenced.

Antiplasticization-driven stiffening in epoxy-amine networks: Effects of the resin formulation

In this work several epoxies with various and structurally related network architectures were prepared using mixtures of a diepoxide resin, a monoepoxide resin, and an aromatic diamine hardener. The effects of the systems formulation on their mechanical and thermal properties were investigated through dynamic-mechanical tests and room temperature tensile testing. The change in glass transition temperature and the stiffening effects measured at room temperature were interpreted at the light of the macromolecular architecture and the chain mobility hindrance connected to the antiplasticization phenomenology.

Effect of shade and thermo-mechanical viscosity stimulation methods on the rheological properties of nanohybrid resin composite

Abstract The aim of the present study is to measure the rheological properties of nanohybrid resin composite of three shades in pre-polymerized phase using different thermomechanical stimulations. Nanohybrid composite (Kerr Herculite XRV Ultra) in enamel, dentin, and incisal shades was included. Rheological measurements were made with a rotational rheometer in dynamic oscillation mode using three methods: (a) Strain Sweep test explored a range of deformation γ0 from 0.025 to 3% with a frequency ω = 1 Hz (temperature set at 25 and 65 °C), (b) Frequency Sweep test explored frequencies between 1 and 100 rad/s applying a deformation γ0 = 0.5% (temperature set at 25; 45; 65 °C), and (c) Ramp Temperature test explored a heating phase from 25 to 75 °C then a cooling phase back to 25 °C applying a γ0 = 0.5% and a ω = 10 rad/s. Data were analyzed using a three-way ANOVA and Tukey’s test (α = 0.05). Viscosity measurement (p < 0.05) and shade of the composites (p < 0.05) significantly affected the results. Viscosity turned out to be subordinate to strain amplitude, frequency, temperature, and axial force applied during each test. Enamel shade was the most viscous whereas dentin shade was 8% less viscous (p < 0.05). The incisal shade was significantly less viscous (70%) than enamel (p < 0.05). Pre-heating decreased viscosity of incisal shade (30%) above 50 °C but this value was 90 and 98%, respectively, for strain and frequency sweep test. Preheating had a side effect as in the cooling phase, viscosity increased from 66 to 450% exceeding the value recorded at the beginning of the test. Preheating was not effective to reduce viscosity, and may reveal some side effects. The composite tested might not be pre-heated above 45 °C.

Rheological Characterization of Ethylcellulose-Based Melts for Pharmaceutical Applications

ABSTRACTRheological characterization of ethylcellulose (EC)-based melts intended for the production, via micro-injection moulding (μIM), of oral capsular devices for prolonged release was carried out. Neat EC, plasticized EC and plasticized EC containing solid particles of a release modifier (filler volume content in the melt around 30%) were examined by capillary and rotational rheometry tests. Two release modifiers, differing in both chemical nature and particle geometry, were investigated. When studied by capillary rheometry, neat EC appeared at process temperatures as a highly viscous melt with a shear-thinning characteristic that progressively diminished as the apparent shear rate increased. Thus, EC as such could not successfully be processed via μIM. Plasticization, which induces changes in the material microstructure, enhanced the shear-thinning characteristic of the melt and reduced considerably its elastic properties. Marked wall slip effects were noticed in the capillary flow of the plasticized EC-based melts, with or without release modifier particles. The presence of these particles brought about an increase in viscosity, clearly highlighted by the dynamic experiments at the rotational rheometer. However, it did not impair the material processability. The thermal and rheological study undertaken would turn out a valid guideline for the development of polymeric materials based on pharma-grade polymers with potential for new pharmaceutical applications of μIM.

Mechanical characterisation and replication quality analysis of micro-injected parts made of carbon nanotube/polyoxymethylene nanocomposites

The increasing demand for small and cheap parts is boosting the development of reliable micro-system technologies. Fabrication process capabilities should expand to encompass a wider range of materials and geometric forms, which can satisfy the specific requirements of new emerging micro-products, and ensure the compatibility of new materials and processing technologies. Polymeric composites are very promising materials, since they offer new combinations of properties not available in traditional homogeneous materials. Because of their advantageous light weight, high strength, fatigue life, and corrosion resistance, they are forecast to replace conventional materials in several applications. Among the plastic process technologies, injection moulding is one of the key technologies for manufacturing miniaturised components due to its mass production capability and relatively low production cost. Micro-injection moulding allows to transfer micron and even submicron precision features to small products. Since final product properties strongly depend on materials and production processes and parameters, the process conditions of compounding as well as of product manufacturing have to be carefully studied and controlled. This is particularly important for the manufacturing of micro-products, since, at the micro-scale, some phenomena negligible at the macro-scale (as hesitation effect or capillarity forces for examples) can become important. However, only few studies concern the micro-injection of nanocomposites. Therefore, in this paper the micro-injection of two composites made of polyoxymethylene and carbon nanotubes has been studied. First, the electrical properties of the compounds have been measured; the fillers are dispersed in the matrix and form a network that dramatically increases the conductivity of the composites in comparison with the pristine resin. Then the compounds have been injected using a micro-injection machine and the components have been analysed. The mechanical analysis, based on tensile tests and dynamic-mechanical experiments on miniaturised dog-bone specimens, shows a slight reinforcing effect of the filler; however, the ductility is considerably reduced. This is likely due to a scarce adhesion of the carbon nanotubes and the polymer and the presence of some agglomerates. Moreover, as expected, the mould temperature affects the mechanical properties of the specimens, probably due to its effect on the internal structure of the solidified materials. The dimensional analyses carried out on micro-rib specimens show that replication capability is increased by the presence of the filler and using high values of the process parameters. Finally, microscopic analyses have been done in order to verify the dispersion and orientation of the fillers in the compounds. These effects have been observed only when high shear rates are involved.

Macroporous hydrogels with tailored morphology and mechanical properties

In this work it is shown that hydroxyethylcellulose (HEC) can be employed for preparing macroporous polyacrylamide (PAAm) hydrogels with tailored morphology and mechanical properties. By changing the HEC content in the reaction mixture hydrogels with different pore sizes and degrees of interconnectivity can be synthesized. The equilibrium swelling ratio in 0.1 M NaCl increases with the amount of HEC employed. Tensile tests run on equilibrated hydrogels show that these materials behave as rubber-like materials. Their mechanical stiffness decreases regularly as the amount of HEC, and therefore their porosity, is increased. A more complex trend is observed for elongation and stress at break, which display a maximum at intermediate contents of HEC.

Superabsorbent Biphasic System Based on Poly(Lactic Acid) and Poly(Acrylic Acid)

In this research work, biocomposites based on crosslinked particles of poly(acrylic acid), commonly used as superabsorbent polymer (SAP), and poly-L-lactic acid (PLLA) were developed to elucidate the role of the filler (i.e., polymeric crosslinked particles) on the overall physico-mechanical behavior and to obtain superabsorbent thermoplastic products. Samples prepared by melt-blending of components in different ratios showed a biphasic system with a regular distribution of particles, with diameter ranging from 5 to 10 μm, within the PLLA polymeric matrix. The polymeric biphasic system, coded PLASA i.e. superabsorbent poly(lactic acid), showed excellent swelling properties, demonstrating that cross-linked particles retain their superabsorbent ability, as in their free counterparts, even if distributed in a thermoplastic polymeric matrix. The thermal characteristics of the biocomposites evidence enhanced thermal stability in comparison with neat PLLA and also mechanical properties are markedly modified by ...

Shape memory behavior of epoxy-based model materials: Tailoring approaches and thermo-mechanical modeling

A series of structurally related epoxy resins were prepared as model systems for the investigation of the shape memory response, with the aim to assess the possibility of tailoring their thermo-mechanical response and conveniently describing their strain evolution under triggering stimuli with a simple thermoviscoelastic model. The resins formulation was varied in order to obtain systems with controlled glass transition temperature and crosslink density. The shape memory response was investigated by means of properly designed thermo-mechanical cycles, which allowed to measure both the ability to fully recover the applied strain and to exert a stress on a confining medium. The results were also compared with the predictions obtained by finite element simulations of the thermo-mechanical cycle by the employ of a model whose parameters were implemented from classical DMA analysis.

The load separation criterion in elastic-plastic fracture mechanics: Rate and temperature dependence of the material plastic deformation function in an ABS resin

This work is aimed at analyzing the effects of temperature and loading rate on the plastic deformation behavior of an acrylonitrile-butadiene-styrene (ABS) resin during a fracture process. According to the load separation criterion, the plastic deformation behavior during the fracture process of an elastic-plastic material is described by a plastic deformation function. For the ABS here examined, the material plastic deformation function was constructed at different temperatures and loading rates, by single edge notched in bending (SEB) tests on blunt notched specimens. Both low and moderately high (impact) loading rates were explored. For the various conditions of temperature and loading rate the material yield stress was also measured by uniaxial tensile tests. The relationships between material deformation function and yield stress were researched and discussed.