Due to its exceptional biocompatibility, Polyurethane (PU) reinforced with calcium carbonate (CaCO3) is a composite material with significant biomedical applications. However, much of the currently known mechanical and chemical information regarding composites has been obtained at low and moderate CaCO3 content levels. This study employs experimental and theoretical tools to evaluate the structural, morphological, and mechanical properties of pristine polyurethane, and when doped with CaCO3 at 25 and 50 wt.%. In the experiments the samples are characterized using X-ray diffraction (XRD), infrared spectrophotometry (FT-IR), scanning electron microscopy (SEM), and tensile and flexural mechanical tests, while theoretical calculations are performed to evaluate the carbonate-polymer interaction. The XRD and FT-IR results indicate that CaCO3 is at the calcite phase and that PU-CaCO3 materials exhibit a broadening of bands related to the NH2 group. This result is explained using theoretical calculations that demonstrate a weak interaction between those molecules with the CaCO3 surface, where the molecule-calcite interaction occurs primarily through the NH2 molecular link. With respect to mechanical behaviour, the results show less fracture resistance and greater stiffness for the materials containing CaCO3, compared to those containing only PU. These results are explained in terms of the stress concentration due to CaCO3 within the polymer. Finally, the results detailed in this paper show that a high calcium carbonate loading is suitable for increasing the rigidity and decreasing the fracture toughness of the biomaterial, in association with a reduction of the plastic region.
The aim of this work is to evaluate the changes in compression properties of a bio-based polyurethane foam after exposure to 90 °C for different periods of time, and to propose a method to extrapolate these results and use a numerical approach to predict the compression behaviour after degradation for untested conditions at different degradation times and temperatures. Bio-based polymers are an important sustainable alternative to oil-based materials. This is explained by the foaming process and the density along the material as it was possible to see in a digital image correlation analysis. After 60 days, stiffness was approximately decreased by half in both directions. The decrease in yield stress due to thermo-oxidative degradation had a minor effect in the foaming directions, changing from 352 kPa to 220 kPa after 60 days, and the transverse property was harshly impacted changing from 530 kPa to 265 kPa. The energy absorption efficiency was slightly affected by degradation. The simulation of the compression stress-strain curves were in accordance to the experimental data and made it possible to predict the changes in mechanical properties for intermediate periods of degradation time. The plateau stress for the unaged foam transverse to the foaming direction presented experimental and numerical values of 450 kPa and 470 kPa, respectively. In addition, the plateau stresses in specimens degraded for 40 days present very similar experimental and numerical results in the same direction, at 310 kPa and 300 kPa, respectively. Therefore, this paper presents important information regarding the life-span and degradation of a green PUF. It provides insights into how compression properties vary along degradation time as function of material operation temperature, according to the Arrhenius degradation equation.
Biodegradable polymers find applications in many market segments. The ability to meet mechanical requirements within a certain time range, after which it degrades and is naturally absorbed, can be used to produce short-term use products that can be easily disposable with less environmental impact. In the segment of medical devices used in regenerative medicine, these materials are used to produce temporary implants that are naturally assimilated by the human body, avoiding a removal surgery. However, the design of these temporary devices still presents great challenges, namely in the verification of the main requirement: the lifetime of the device, associated with the progressive loss of mechanical properties, until its complete erosion and assimilation. Thus, in this study, a numerical approach is proposed to simulate the polymeric device’s mechanical behavior during its hydrolytic degradation by combining the hydrolysis kinetics, that depends on mechanical factors and promotes a decrease of molecular weight and consequent decrease of mechanical performance, and erosion, when molecular weight reaches a threshold value and the polymer becomes soluble and diffuses outward, resulting in mass loss and decreasing cross-sectional area, which also contributes to the mechanical performance reduction of the device. A phenomenological approach, using the combination of continuum-based hydrolytic damage for the evolution of mechanical properties that depends on the stress field and further removal of the degraded element (to simulate mass loss) was used. Both elastoplastic and hyperelastic constitutive models were applied on this study, where the material model parameters locally depend on the molecular weight.
Compression and morphological evaluation of a new bio-based polyurethane foam (PUF) with aluminum hydroxide (ATH) added as flame retardant were carried out. The PUF was obtained from a blend of vegetable oils. Compression behavior of the polyurethane with different mass fractions of flame retardant (ATH) was investigated according to ASTM D1621–16. The ATH addition highly increased the compression yield strength of the specimens, going from 0.85 MPa (no ATH) to 2.34 MPa ( + 50%wt ATH). The compression yield strain did not show a noteworthy difference up to 40% ATH, presenting a significant decrement in the PUF + 50%ATH. The compression elasticity modulus increased from 15.40 MPa (no ATH) up to 139.77 MPa ( + 50%wt ATH). SEM images were used in order to evaluate the morphological structure of the foam. Regarding the cell sizes, there was no pattern observed, therefore, the cell sizes were adopted as random. The shapes of the cells were detected as elliptical in two different directions in the same cross-sectional area. The digital image correlation (DIC) technique showed higher strain values where the transverse ellipsoid-shaped cells were located, therefore, the load-oriented ellipsoids presented higher stiffness. Thus, the results for PUF with addition of ATH show that the bio-based material presented an important improvement in the compression properties, which allows this material to become more useful for different applications, such as furniture, building and automobile industries, as well as sandwich structures.
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