RESUMEN

Unsaturated polyester resin (UPR) systems are extensively used in composite materials for applications in the transportation, marine, and infrastructure sectors. There are continually evolving formulations of UPRs that need to be evaluated and optimized for processing. Differential Scanning Calorimetry (DSC) provides valuable insight into the non-isothermal and isothermal behavior of UPRs within a prescribed temperature range. In the present work, non-isothermal DSC tests were carried out between temperatures of 0.0 °C and 250 °C, through different heating and cooling ramp rates. The isothermal DSC tests were carried out between 0.0 and 170 °C. The instantaneous rate of cure of the tested temperatures were measured. The application of an autocatalytic model in a calculator was used to simulate curing behaviors under different processing conditions. As the temperature increased from 10 °C up to 170 °C, the rate of cure reduced, and the heat of reaction increased. The simulated cure behavior from the DSC data showed that the degree of cure (α) maximum value of 71.25% was achieved at the highest heating temperature of 85 °C. For the low heating temperature, i.e., 5 °C, the maximum degree of cure (α) did not exceed 12% because there was not enough heat to activate the catalyst to crosslink further.

RESUMEN

Bisphenol A epoxy resin cured with a mixture of dimerized and trimerized fatty acids is the first epoxy vitrimer and has been extensively studied. However, the cure behavior and thermal and mechanical properties of this epoxy vitrimer depend on the epoxy/acid stoichiometry. To address these issues, epoxy vitrimers with three epoxy/acid stoichiometries (9:11, 1:1 and 11:9) were prepared and recycled four times. Differential scanning calorimetry (DSC) was used to study the cure behavior of the original epoxy vitrimers. The dynamic mechanical properties and mechanical performance of the original and recycled epoxy vitrimers were investigated by using dynamic mechanical analysis (DMA) and a universal testing machine. Furthermore, the reaction mechanism of epoxy vitrimer with different epoxy/acid stoichiometry was interpreted. With an increase in the epoxy/acid ratio, the reaction rate, swelling ratio, glass transition temperature and mechanical properties of the original epoxy vitrimers decreased, whereas the gel content increased. The recycling decreased the swelling ratio and elongation at break of the original epoxy vitrimers. Moreover, the elongation at break of the recycled epoxy vitrimers decreased with the epoxy/acid ratio at the same recycling time. However, the gel content, tensile strength and toughness of the original epoxy vitrimers increased after the recycling. The mechanical properties of epoxy vitrimers can be tuned with the variation in the epoxy/acid stoichiometry.

Asunto(s)

Ácidos , Resinas Epoxi , Resinas Epoxi/química , Ácidos Grasos/química , Temperatura , Resistencia a la Tracción

RESUMEN

Curing deformation prediction plays an important role in guiding the tools, curing process design, etc. Analytical methods can provide a rapid prediction and in-depth understanding of the curing deformation mechanism. In this paper, an analytical model is presented to study the cure-induced deformation of composite laminates. Based on the classical laminate theory, the thermal stress and deformation of composites during the curing process are calculated by considering the evolution of the mechanical properties of resin. Additionally, the coupling stiffness of the laminate is taken into consideration in the analytical model. An interface layer between the tool and the part is developed to simulate the variation of the tool-part interaction with the degree of resin cure. The maximum curing deformations and deformation profiles of different lay-up composite parts predicted by the proposed model are compared with the results of the finite element method and previous literature reports. Then, a comprehensive parametric study is carried out to investigate the influence of curing cycle, geometry, tool thermal expansion, and resin characteristics on the curing deformation of composite parts. The results reveal that geometry has a significant influence on the curing deformation of composite parts, but for dimensionally determined parts, curing deformation is mainly attributable to their own anisotropy in macro and micro aspects, as well as the stretching effect of the tool on the part. The percentage contribution of different factors to curing deformation composites with different lay-ups and geometries is also discussed.

RESUMEN

Cure-induced deformations are inevitable in pultruded composite profiles due to the peculiarities of the pultrusion process and usually require the use of costly shimming operations at the assembly stage for their compensation. Residual stresses formed at the production and assembly stages impair the mechanical performance of pultruded elements. A numerical technique that would allow the prediction and reduction of cure-induced deformations is essential for the optimization of the pultrusion process. This study is aimed at the development of a numerical model that is able to predict spring-in in pultruded L-shaped profiles. The model was developed in the ABAQUS software suite with user subroutines UMAT, FILM, USDFLD, HETVAL, and UEXPAN. The authors used the 2D approach to describe the thermochemical and mechanical behavior via the modified Cure Hardening Instantaneous Linear Elastic (CHILE) model. The developed model was validated in two experiments conducted with a 6-month interval using glass fiber/vinyl ester resin L-shaped profiles manufactured at pulling speeds of 200, 400, and 600 mm/min. Spring-in predictions obtained with the proposed numerical model fall within the experimental data range. The validated model has allowed authors to establish that the increase in spring-in values observed at higher pulling speeds can be attributed to a higher fraction of uncured material in the composite exiting the die block and the subsequent increase in chemical shrinkage that occurs under unconstrained conditions. This study is the first one to isolate and evaluate the contributions of thermal and chemical shrinkage into spring-in evolution in pultruded profiles. Based on this model, the authors demonstrate the possibility of achieving the same level of spring-in at increased pulling speeds from 200 to 900 mm/min, either by using a post-die cooling tool or by reducing the chemical shrinkage of the resin. The study provides insight into the factors significantly affecting the spring-in, and it analyzes the methods of spring-in reduction that can be used by scholars to minimize the spring-in in the pultrusion process.

RESUMEN

In this paper, an alternative curing strategy, based on the application of an electric field, is proposed to harden nano-filled multifunctional resins. The resin is obtained through the dispersion of carbon nanotubes, which act as nanometric heater elements in the epoxy matrix. The electro-curing is activated by applying an external electric voltage, which allows tunable cross-linking within the epoxy matrix entrapped between the nanotubes. The electro-curing method allows reaching higher curing degrees with respect to the conventional ones and, consequently, higher glass transition temperatures. This is a direct consequence of the fact that the curing reactions start directly in the regions at the interphase between carbon nanotubes, acting as heater nano-filaments, and the polymeric matrix. The proposed method is able to give composites better properties, making the curing process fast and energy-saving.

RESUMEN

Post-curing is intended to improve strength, elevate glass transition, and reduce residual stress and outgassing in thermosets. Also, experiments indicate post-curing temperatures lead to ether crosslinks and backbone dehydration. These results informed molecular dynamics methods to represent them and compare the resulting thermomechanical effects. Diglycidyl ether of bisphenol A (DGEBA)-diamino diphenyl sulfone (DDS) systems were examined. Independent variables were resin length, stoichiometry, and reaction type (i.e., amine addition, etherification, and dehydration). Etherification affected excess epoxide systems most. These were strengthened and became strain hardening. Systems which were both etherified and dehydrated were most consistent with results of post-curing experiments. Dehydration stiffened and strengthened systems with the longer resin molecules due to their intermediate hydroxyl groups for crosslinking. Changes in the concavity of functions fit to the specific volume versus temperature were used to detect thermal transitions. Etherification generally increased transition temperatures. Dehydration resulted in more transitions.