Search Results (15)

Asphalt is a widely used polymeric material in pavement engineering. However, it is easily affected by heat and ultraviolet rays, which accelerate its molecular degradation and physicochemical aging, thereby limiting its service life. To improve the anti-aging properties of asphalt, three types of nano-zinc oxide (ZnO)-modified asphalt were prepared. The chemo-rheological behavior, structural evolution of polymeric components, molecular weight distribution, and nanoscale morphology of nano-ZnO-modified asphalt were studied via dynamic shear rheometry (DSR), Fourier transform infrared spectrometry (FTIR), gel permeation chromatography (GPC) and atomic force microscopy (AFM), and the aging resistance of nano-ZnO-modified asphalt was quantitatively analyzed using the rutting factor index, functional group index, molecular size ratio, and nanoscale parameters. The findings indicate that nano-ZnO enhances the high-temperature rheological properties of asphalt and delays the increase in the rutting factor of aged asphalt. Nano-ZnO is dispersed in the asphalt matrix in the form of a physical mixture without inducing new chemical bonds, and can reduce the nanoscale roughness of asphalt. After aging, the nanoscale roughness and the aspect ratio of the bee structure decreased, and the bee structure area increased. According to the changes in the functional group index and the proportions of molecular sizes in the asphalt, it was found that nano-ZnO can significantly improve asphalt’s aging resistance. The results of this study provide insights into the nanoscale modification and structure–property relationships of polymeric asphalt binders, providing a reference for the design and application of functional polymer nanocomposite systems with improved durability. Full article

Subsurface mass concrete infrastructure—including immersed tunnels, dams, and nuclear waste containment systems—frequently faces calcium-leaching risks from prolonged groundwater exposure. An anisotropic stress-leaching damage model incorporating microcrack propagation is developed for underground concrete’s chemo–mechanical coupling. This model investigates stress-induced anisotropy in concrete through the evolution of oriented microcrack networks. The model incorporates nonlinear anisotropic plastic strain from coupled chemical–mechanical damage. Unlike conventional concrete rheology, this model characterizes chemical creep through stress-chemical coupled damage mechanics. The numerical model is incorporated within COMSOL Multiphysics to perform coupled multiphysics simulations. A close match is observed between the numerical predictions and experimental findings. Under high stress loads, calcium leaching and mechanical stress exhibit significant coupling effects. Regarding concrete durability, chemical degradation has a more pronounced effect on concrete’s stiffness and strength reduction compared with stress-generated microcracking. Full article

Fibre deformation (or shearing of yarns) can develop during the liquid moulding of composites due to injection pressures or polymerisation (cross-linking) reactions (e.g., chemical shrinkage). On that premise, this may also induce potential residual stress–strain, warpage, and design defects in the composite part. In this paper, a developed numerical framework is customised to analyse deformations and the residual stress–strain of fibre (at a micro-scale) and yarns (at a meso-scale) during a liquid composite moulding (LCM) process cycle (fill and cure stages). This is achieved by linking flow simulations (coupled filling–curing simulation) to a transient structural model using ANSYS software. This work develops advanced User-Defined Functions (UDFs) and User-Defined Scalers (UDSs) to enhance the commercial CFD code with extra models for chemorheology, cure kinetics, heat generation, and permeability. Such models will be hooked within the conservation equations in the thermo-chemo-flow model and hence reflected by the structural model. In doing so, the knowledge of permeability, polymerisation, rheology, and mechanical response can be digitally obtained for more coherent and optimised manufacturing processes of advanced composites. Full article

This paper analyzes the effect of crosslinking reactions on a thermoset polymer’s viscoelastic properties. In particular, a numerical model to predict the evolution of epoxy’s mechanical properties during the curing process is proposed and implemented in an Ansys APDL environment. A linear viscoelastic behavior is assumed, and the scaling of viscoelastic properties in terms of the temperature and degree of conversion is modeled using a modified version of the TNM (Tool–Narayanaswamy–Mohynian) model. The effects of the degree of conversion and structural relaxation on epoxy’s relaxation times are simultaneously examined for the first time. This formulation is based on the thermo-rheological and chemo-rheological simplicities hypothesis and can predict the evolution of epoxy’s relaxation phenomena. The thermal–kinetic reactions of curing are implemented in a homemade routine written in APDL language, and the structural module of Ansys is used to predict the polymer’s creep and stress relaxation curves at different temperatures and degrees of conversion. Full article

The present numerical study proposes a framework to determine the heat flow parameters—specific heat and thermal conductivity—of resin–graphene nanoplatelets (GNPs) (modified) as well as non-modified resin (with no GNPs). This is performed by evaluating the exothermic reaction which occurs during both the filling and post-filling stages of Liquid Composite Moulding (LCM). The proposed model uses ANSYS Fluent to solve the Stokes–Brinkman (momentum and mass), energy, and chemical species conservation equations to a describe nano-filled resin infusion, chemo-rheological changes, and heat release/transfer simultaneously on a Representative Volume Element (RVE). The transient Volume-of-Fluid (VOF) method is employed to track free-surface propagation (resin–air interface) throughout the computational domain. A User-Defined Function (UDF) is developed together with a User-Defined Scaler (UDS) to incorporate the heat generation (polymerisation), which is added as an extra source term into the energy equation. A separate UDF is used to capture intra-tow (microscopic) flow by adding a source term into the momentum equation. The numerical findings indicate that the incorporation of GNPs can accelerate the curing of the resin system due to the high thermal conductivity of the nanofiller. Furthermore, the model proves its capability in predicting the specific heat and thermal conductivity of the modified and non-modified resin systems utilising the computed heat of reaction data. The analysis shows an increase of ∼15% in the specific heat and thermal conductivity due to different mould temperatures applied (110–170 °C). This, furthermore, stresses the fact that the addition of GNPs (0.2 wt.%) improves the resin-specific heat by $3.68\%$ and thermal conductivity by $58\%$ in comparison to the non-modified thermoset resin. The numerical findings show a satisfactory agreement with and in the range of experimental data available in the literature. Full article

Alkaline sodium hydroxide/sodium silicate-activating high-purity metakaolin geopolymerization is described in terms of metakaolin deconstruction in tetrahedral hydrate silicate [O[Si(OH)₃]]⁻ and aluminate [Al(OH)₄]⁻ ionic precursors followed by their reassembling in linear and branched sialates monomers that randomly copolymerize into an irregular crosslinked aluminosilicate network. The novelty of the approach resides in the concurrent thermo-calorimetric (differential scanning calorimetry, DSC) and rheological (dynamic mechanical analysis, DMA) characterizations of the liquid slurry during the transformation into a gel and a structural glassy solid. Tests were run either in temperature scan (1 °C/min) or isothermal (20 °C, 30 °C, 40 °C) cure conditions. A Gaussian functions deconvolution method has been applied to the DSC multi-peak thermograms to separate the kinetic contributions of the oligomer’s concurrent reactions. DSC thermograms of all tested materials are well-fitted by a combination of three overlapping Gaussian curves that are associated with the initial linear low-molecular-weight (Mw) oligomers (P1) formation, oligomers branching into alumina-rich and silica-rich gels (P2), and inter- and intra-molecular crosslinking (P3). The loss factor has been used to define viscoelastic behavioral zones for each DMA rheo-thermogram operated in the same DSC thermal conditions. Macromolecular evolution and viscoelastic properties have been obtained by pairing the deconvoluted DSC thermograms with the viscoelastic behavioral zones of the DMA rheo-thermograms. Two main chemorheological behaviors have been identified relative to pre- and post-gelation separation of the viscoelastic liquid from the viscoelastic solid. Each comprises three behavioral zones, accounting for the concurrently occurring linear and branching oligomerization, aluminate-rich and silica-rich gel nucleations, crosslinking, and vitrification. A “rubbery plateau” in the loss factor path, observed for all the testing conditions, identifies a large behavioral transition zone dividing the incipient gelling liquid slurry from the material hard setting and vitrification. Full article

Automated fiber placement is a state-of-the-art manufacturing method which allows for precise control over layup design. However, AFP results in irregular morphology due to fiber tow deposition induced features such as tow gaps and overlaps. Factors such as the squeeze flow and resin bleed out, combined with large non-linear deformation, lead to morphological variability. To understand these complex interacting phenomena, a coupled multiphysics finite element framework was developed to simulate the compaction behavior around fiber tow gap regions, which consists of coupled chemo-rheological and flow-compaction analysis. The compaction analysis incorporated a visco-hyperelastic constitutive model with anisotropic tensorial prepreg viscosity, which depends on the resin degree of cure and local fiber orientation and volume fraction. The proposed methodology was validated using the compaction of unidirectional tows and layup with a fiber tow gap. The proposed approach considered the effect of resin bleed out into the gap region, leading to the formation of a resin-rich pocket with a complex non-uniform morphology. Full article

Although geopolymers, as structural materials, should have superior engineering properties than traditional cementitious materials, they often need to improve their final characteristics’ reproducibility due to the need for more control of the complex silico-aluminate decomposition and polymerisation stages. Thermosetting of a reactive geopolymeric paste involves tetrahedral Silicate and Aluminate precursor condensation into polyfunctional oligomers of progressively higher molecular weight, transforming the initial liquid into a gel and a structural solid. Viscosity and gelation control become particularly critical when the geopolymer is processed with 3D printing additive technology. Its physical state modification kinetics should match the flow and setting characteristics required by the deposition process. The reaction kinetics and the elastic and viscous characteristics preceding gelation and hardening have been investigated for an alkali-activated Metakaolin/Sodium Silicate-Sodium Hydroxide paste with a Si/Al ratio > 3. A chemoreological approach has been extended to these inorganic polymerisable systems, as already utilised for organic thermosetting polymers. Differential scanning calorimetry and Oscillatory DMA were carried out to monitor the advancement of the polymerisation reaction and the associated variations of the rheological viscoelastic properties. Dynamic thermal scans were run at 1 °C/min and a frequency of 10 Hz for the dynamic mechanical tests. The observed kinetics of polymerisation and variations of the elastic and viscous components of the complex viscosities and shear moduli are described in terms of polycondensation of linear and branched chains of oligomeric macromolecules of increasing complexity and molecular weight up to gelation (Gel1) and cross-linking of the gelled macrostructure (Gel2) and final glassy state. Geopolymerization can be allocated into two main behavioural zones: a viscoelastic liquid paste below 32.5% of reaction advancement and a viscoelastic solid above. Initial complex viscosities range from 2.3 ± 0.9  × 10⁻⁵ MPa_*s to 6.8 ± 0.9  × 10⁻² in the liquid-like state and from 1.9 ± 0.1 MPa to 9.6 ± 2.1 × 10² MPa in the solid-like state. Full article

In this study, the curing kinetics of epoxy nanocomposites containing ultra-fine full-vulcanized acrylonitrile butadiene rubber nanoparticles (UFNBRP) at different concentrations of 0, 0.5, 1 and 1.5 wt.% was investigated. In addition, the effect of curing temperatures was studied based on the rheological method under isothermal conditions. The epoxy resin/UFNBRP nanocomposites were characterized via Fourier transform infrared spectroscopy (FTIR). FTIR analysis exhibited the successful preparation of epoxy resin/UFNBRP, due to the existence of the UFNBRP characteristic peaks in the final product spectrum. The morphological structure of the epoxy resin/UFNBRP nanocomposites was investigated by both field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) studies. The FESEM and TEM studies showed UFNBRP had a spherical structure and was well dispersed in epoxy resin. The chemorheological analysis showed that due to the interactions between UFNBRP and epoxy resin, by increasing UFNBRP concentration at a constant temperature (65, 70 and 75 °C), the curing rate decreases at the gel point. Furthermore, both the curing kinetics modeling and chemorheological analysis demonstrated that the incorporation of 0.5% UFNBRP in epoxy resin matrix reduces the activation energy. The curing kinetic of epoxy resin/UFNBRP nanocomposite was best fitted with the Sestak–Berggren autocatalytic model. Full article

Co-bonding is an effective joining method for fiber-reinforced composites in which a prefabricated part bonds with a thermoset resin during the curing process. Manufacturing of co-bonded thermoset-thermoplastic hybrid composites is a challenging task due to the complexities of the interdiffusion of reactive thermoset resin and thermoplastic polymer at the interface between two plies. Herein, the interphase properties of co-bonded acrylonitrile butadiene styrene thermoplastic to unsaturated polyester thermoset are investigated for different processing conditions. The effect of processing temperature on the cure kinetics and interdiffusion kinetics are studied experimentally. The interphase thickness and microstructure are linked to the chemo-rheological properties of the materials. The interdiffusion mechanisms are explored and models are developed to predict the interphase thickness and microstructure for various process conditions. The temperature-dependent diffusivities were estimated by incorporating an inverse diffusion model. The mechanical response of interphases was analyzed by the Vickers microhardness test and was correlated to the processing condition and microstructure. It was observed that processing temperature has significant effect on the interdiffusion process and, consequently, on the interphase thickness, its microstructure and mechanical performance. Full article

Liquid resin infusion processes are becoming attractive for aeronautic applications as an alternative to conventional autoclave-based processes. They still present several challenges, which can be faced only with an accurate simulation able to optimize the process parameters and to replace traditional time-consuming trial-and-error procedures. This paper presents an experimentally validated model to simulate the resin infusion process of an aeronautical component by accounting for the anisotropic permeability of the reinforcement and the chemophysical and rheological changes in the crosslinking resin. The input parameters of the model have been experimentally determined. The experimental work has been devoted to the study of the curing kinetics and chemorheological behavior of the thermosetting epoxy matrix and to the determination of both the in-plane and out-of-plane permeability of two carbon fiber preforms using an ultrasonic-based method, recently developed by the authors. The numerical simulation of the resin infusion process involved the modeling of the resin flow through the reinforcement, the heat exchange in the part and within the mold, and the crosslinking reaction of the resin. The time necessary to fill the component has been measured by an optical fiber-based equipment and compared with the simulation results. Full article

Products made of polyurethane foam are manufactured by the chemical reaction of various low-viscosity raw materials and additives. The diversity of different formulations to meet the requirements of the market makes the characterization of their processing and flow properties important for a simple and error-free production. The modeling and simulation of such processes are equally of great importance. This provides additional findings without the expense of real tests and makes it easier to design components. The work described in this paper was carried out against this background. An experimental setup using a rheometer was developed to determine the flow and curing properties of reacting polyurethane foam reproducibly with comparable expansion conditions to industrial processes. The experiment was mathematically modelled to investigate the rheology of reacting polyurethane foams. The mathematical framework consists of coupled, non-linear, partial differential equations for the dynamics and the heat transfer processes in the system. These are solved numerically in 3D using finite volume techniques under adequate physical conditions. The accuracy of two viscosity laws according to the state of the art and their novel combination were investigated in this context. The proposed viscosity model of this study provides accurate results compared to the experiment. Full article

Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (E_α-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower E_α. The shift from chemical to diffusion control was also estimated. Full article

This paper computationally investigates heterogeneity in the distribution of foam fraction in chemically expanding blown polyurethane foam. The experimentally observed disparity in the volumes of expanded foam when an equal mass of the foaming mixture was injected into tubes of different dimensions motivated this study. To understand this phenomenon, attributed to local variations in the thermal and rheological properties of the expanding system, we explore available data from free-rise foam-expansion experiments in different geometries. Inspired by the mathematical framework for the microstructure modelling of bubble growth in viscous liquids, we study the reacting mixture as a continuum and formulate appropriate mathematical models that account for spatial inhomogeneity in the foam-expansion process. The nonlinear coupled system of partial differential equations governing flow was numerically solved using finite-volume techniques, and the associated results are presented and discussed with graphical illustrations. The proximity of the foaming-mixture core to the external environment and the thickness of a thermal-diffusion layer formed near the bounding geometry was seen to influence the distribution of the foam fraction. Our simulations showed an average spatial variation of about 1.1% in the distribution of solid foam fraction from the walls to the core, as verified with data from $\mu$ CT scan analysis of the expanded foam. This also reflects the distribution of void fraction in the foam matrix. The models were validated with experimental data, and our results favourably compared with the experiment observations. Full article

A considerable amount of research has been conducted to determine how cell walls are loosened to produce irreversible wall deformation and expansive growth in plant and algal cells. The same cannot be said about fungal cells. Almost nothing is known about how fungal cells loosen their walls to produce irreversible wall deformation and expansive growth. In this study, anoxia is used to chemically isolate the wall from the protoplasm of the sporangiophores of Phycomyces blakesleeanus. The experimental results provide direct evidence of the existence of chemistry within the fungal wall that is responsible for wall loosening, irreversible wall deformation and elongation growth. In addition, constant-tension extension experiments are conducted on frozen-thawed sporangiophore walls to obtain insight into the wall chemistry and wall loosening mechanism. It is found that a decrease in pH to 4.6 produces creep extension in the frozen-thawed sporangiophore wall that is similar, but not identical, to that found in frozen-thawed higher plant cell walls. Experimental results from frozen-thawed and boiled sporangiophore walls suggest that protein activity may be involved in the creep extension. Full article