Yield Stress Values Research Articles

COMPUTATIONAL-EXPERIMENTAL METHOD FOR STRESS-STRAIN CURVE CONSTRUCTING UNDER CONDITIONS OF INHOMOGENEOUS STRESS FIELDS

In order to ensure reliability of structures, it is necessary to study equilibrium damage accumulation which initiates softening zones in solids. It is considered appropriate to use postcritical deformation models when conducting strength analysis of structures. However, obtaining complete stress-strain curves in standard tests is difficult due to the strain localization in the form of a neck. At the same time, the use of true stresses taking into account changes in a specimen cross section is incorrect due to the implementation of a complex stress state. In this regard, it is necessary to develop computational and experimental methods for constructing material stress-strain curves under conditions of inhomogeneous stress fields. In this case it seems reasonable to use data on strain fields on the body’s surface, which can be obtained, for example, using non-contact optical video systems. The paper presents the computational-experimental method for constructing a stress-strain curve under conditions of inhomogeneous stress fields. An elastoplastic model of an isotropic material is considered. The initial data of the method are two elastic constants, the yield stress value, the load diagram of a body with a stress concentrator, and the maximum values of strain intensity corresponding to various states. The developed method was tested by a numerical simulation of deforming an hourglass specimen and a plate with a stress concentrator. Stress-strain curves with and without a yield plateau are considered. The results demonstrate a high agreement between the initially specified and reconstructed stress-strain curves. A conclusion is made about the rationality of using the developed method when constructing stress-strain diagrams and necessity for its modernization to describe the postcritical deformation stage.

Investigation of fresh and hardened properties of 3D printable concrete containing ozone-modified carbon fiber

In this study, the effect of using carbon fiber surface modified with ozone on the fresh-hardened state properties, high temperature resistance and rheological properties of 3D printable concrete (3DPC) was investigated. A total of 7 different 3DPC were prepared by adding modified and unmodified carbon fibers to the mixture at different ratios. Fiber surface modification was characterized by XPS analysis. The modification process improves the fiber/matrix adherence of 3DPC mixtures, resulting in an increase in compressive strength. The flexural strength of the mixtures increases with fiber modification, regardless of the fiber utilization ratio. Dynamic yield stress and apparent viscosity values of the mixtures decreased with the increase in fiber utilization ratio. τ3.p/τ2.p and Athix methods are more suitable for comparing the thixotropic properties of 3DPC mixtures with modified fibers suitable for comparing the thixotropic properties of 3DPC mixtures with modified fibers.

Influence of Grinding Aids on the Grinding Performance and Rheological Properties of Cementitious Systems.

The cement industry is of great importance in terms of raw materials consumed, energy consumed, and greenhouse gases emitted. Grinding aids (GA) are used to reduce energy consumption and costs, as well as to reduce the amount of CO2 released into the environment. In this study, the effect of GA-polycarboxylate ether-based water-reducing admixture (PCE) compatibility on some fresh, rheological and hardened state properties of cementitious systems was investigated. In order to investigate the rheological properties and thixotropic behavior of the mixtures, a total of 51 cement paste mixtures were prepared, containing 4 different types (molasses, MEG, DEA and ethanol) and ratios (0.025, 0.05, 0.75 and 0.1) of GAs and 2 different ratios (0.08% and 0.16%) of PCE in addition to the control mixture. In addition, the effect of the used GAs on the grinding efficiency and compressive strength value was investigated. Additionally, the predictability of the type of GA, dosage and cure time using the Taguchi method was investigated. It was determined that the highest grinding performance was obtained in mixtures containing MEG. It was determined that in cement paste mixtures containing GAs, the dynamic yield stress and viscosity values generally decrease with the increase in PCE usage rate up to a certain value, and these values may increase if the PCE usage increases further. It was determined that such behavior is not present in cement paste mixtures containing GAs and that the structural build-up value of the mixtures generally increases with the increase in the PCE admixture usage rate. It was determined that the use of GAs had a positive effect on 28-day compressive strength.

Development of geopolymer and cement-based shotcrete mortar: Impact of mix design parameters and spraying process

Shotcrete mortar is used in various construction works, including repair, tunneling, mining, and slope stabilization, among others. Traditionally, cement is used to produce shotcrete mortars with high viscosity, flowability, and early strength. Geopolymers (GP) have the potential to replace cement in shotcrete mortars, owing to their ability to reduce the material’s environmental footprint without compromising performance. This investigation assesses the feasibility of utilizing fly ash and blast furnace slag-based GP mortars produced with dune sand in shotcrete applications while comparing them to cement-based mixtures. The GP and cement-based shotcrete mortars were designed to have similar yield stress values. The evaluated properties included the initial flow, thickness layer, rebound material, rheological properties, setting time, compressive strength, ultrasonic pulse velocity, and pull-off bonding strength. Test results showed direct relationships between the yield stress and initial flow values, as well as between the buildup thickness and plastic viscosity, revealing that GP mortars were suitable for shotcrete applications, specifically those produced with flow values of 18.5 cm or less. GP mixtures produced with higher slag content than fly ash, higher sand content compared to binder, higher SH molarity, and lower solution content achieved higher buildup thickness owing to their higher viscosity. In the second phase, the performance of four mixes with different initial flows was assessed at various pumping flow rates and distances between the wall and machine pipe nozzle. The findings confirmed that these spraying parameters are crucial to improve the shotcrete performance of GP mortar with varying fresh behaviors.

Lattice-designed 3D printing of gluten-free pasta incorporated with xanthan gum for the elderly food

The use of xanthan gum (XG) has been reported to soften the texture of gluten-free pasta (GFP), making it an ideal food for the elderly with swallowing difficulties. Designing pasta shapes can enhance the suitability of sauces, improving sensory properties. This study aimed to investigate the optimal amount of XG for softening the texture of GFP. Three-dimensional (3D) printing was used to create lattice design shapes of the soft GFP, and sauce adhesion capacity (SAC) was investigated. The viscoelastic properties and yield stress values of the GFP dough significantly increased with higher XG contents (0.25%–2%) (p < 0.05), improving ink printability. The X-1% sample showed a decrease in the storage modulus (G’) (representing solid-like behavior) curve when the temperature increased from 68 °C, correlating with its lower hardness (5.11 × 104 ± 480 N/m2), which almost matched level 2 as the soft solid food that can be mashed with gums. This also agreed with its reduction in water-holding capacity (WHC) and its larger microstructural porosities. The SAC test demonstrated a significant relationship between 3D lattice design shapes and sauce viscosity, concluding that high- or low-viscous sauces may be suitable for the larger or smaller size of interior hole designs, respectively. This study provides guidance for developing novel 3D-printed GFP with a soft texture specifically designed to improve the mealtime experience for the elderly.

Microstructural and rheological influence of different strategies to mitigate oil migration in chocolate pralines during storage in limiting conditions

Chocolate pralines are metastable systems in which oil migration, particularly at high storage temperatures, represents the main contributor to quality loss. In this study, two strategies were compared to retard this migration respect to a control sample (C); the use of a barrier consisting of cocoa butter high-melting (CB) and the use of an oleogel realized with beeswax and sunflower oil (CA). Samples were stored in thermal abuse conditions (28 °C) and subjected to: microstructural, rheological and ability to retain oil in the filling analysis and colorimetric evaluation. Microstructure highlighted the highest percentages of oil in CA samples filling during storage, respect to C and CB, as confirmed by oil release. According to fundamental rheological analysis, C and CB showed the highest filling yield stress values respect to CA, which showed a linear and homogenous trend. Dynamic rheological analysis underlined the presence of an increase in the elastic modulus during storage, suggesting matrix aggregation and gummy filling cream, which was lowest for CA, supporting the positive effect exhibited by this barrier. For empirical-imitative analysis, CA showed a more spreadable and creamy filling. Results revealed the ability of beeswax oleogels to improve quality attributes of pralines during storage, also at higher temperatures.

Discrepancies in dynamic yield stress measurements of cement pastes

The dynamic yield stress associated with the flow cessation of cement pastes is measured using a rheometer equipped with various shear geometries such as vane, helical, sandblasted co-axial cylinders, and serrated parallel plates, as well as with the mini-cone spread test. Discrepancies in yield stress values are observed for cement pastes at various volume fractions, with one to two orders of magnitude difference between vane, helical and mini-cone spread measurements on the one hand, and co-axial cylinder and parallel plate measurements on the other hand. To understand this discrepancy, the flow profile of a cement paste in the parallel-plate geometry is investigated with a high-speed camera, revealing the rapid formation of an un-sheared band near the static bottom plate. The width of this band depends upon the rotational velocity of the top plate, and upon the shear time. Recalculation of shear stress shows that the reduced sheared gap alone cannot explain the low measured yield stress. Further exploration suggests the formation of zones with lower particle content, possibly linked to cement particle sedimentation. Here, we argue that the complex nature of cement pastes, composed of negatively buoyant non-Brownian particles with attractive interactions due to highly charged nano-size hydration products, accounts for their complex rheological behavior.Graphical abstract

Effect of V Content on the Microstructure and Mechanical Properties of High‐Pressure Torsion Nanostructured CoCrFeMnNiVx High‐Entropy Alloys

The article presents investigations of microstructure and low‐temperature mechanical properties of nanostructured alloys CoCrFeMnNiVx (x = 0.15–0.75), processed by high‐pressure torsion (HPT) at temperatures of 300 and 77 K. While at x ≥ 0.5 the values of microhardness (Hv) and compression yield stress (σ0.2) in samples after HPT at 77 K are larger than those in samples after HPT at 300 K, for x ≤ 0.2 surprisingly the opposite effect is observed. As in case of the undeformed CoCrFeMnNiVx alloys, the behavior for vanadium concentrations x ≥ 0.5 can be related to the formation of tetragonal σ‐phase in addition to face‐centered cubic matrix, while the anomalous behavior for x ≤ 0.2 arises from the formation of HPT‐induced hexagonal martensitic phase. In the low‐temperature ranges, i.e., 20–300 K in case of HPT nanostructured CoCrFeMnNiV0.2, and 150–300 K in case of HPT nanostructured CoCrFeMnNiV0.5, dependences of σ0.2(T) show characteristics of thermally activated dislocation movement. For the first time in high‐entropy alloys, anomalous dependences of σ0.2(T) at temperatures 4.2–20 K for CoCrFeMnNiV0.2, and at 80–150 K for CoCrFeMnNiV0.5 are found, which indicate at the occurrence of nonthermal inertial dislocation movement.

Technological aspects and requirements to raw materials for increasing the nutritional value of glaze

Glaze, giving confectionery products an aesthetically attractive appearance, provides the possibility of prolonging their shelf life. The main raw components of the glaze are sugar and fat, which determines its high caloric content. Modern trends dictate the need to create confectionery products enriched with essential nutrients found in vegetables, berries and fruits. The introduction of finely ground additives in the form of fruit and vegetable powder into the glaze formulation may entail changes in the rheological and crystallization properties of the glaze. The aim of the research is to develop technological methods of fruit and vegetable confectionery glaze production with increased content of dietary fibers and reduced amount of added sugar, as well as to establish requirements for fruit and vegetable powders as raw materials used in the production of confectionery glaze. The objects of the research were industrial samples of fruit and vegetable powders from raspberry, apple, carrot and beet, as well as samples of confectionery glaze produced in laboratory conditions. Common and special research methods were used in the work. The technological acceptability of using fruit and vegetable powders in the production of confectionery glaze according to their physical and chemical parameters has been determined. The yield stress of the glaze increased as the content of fruit and vegetable powder increased from 3 to 15% to varying degrees depending on its fat-absorbing capacity. The crystallization characteristic of the glaze changed: the solidification temperature decreased by 1-2 °C, the crystallization duration increased by 27-40% compared to the control sample. The nomenclature is substantiated and numerical values of quality criteria of fruit and vegetable powders to ensure technological properties of glaze are given. The influence of step-by-step introduction of surfactants on the value of yield stress of confectionery glazes with fruit and vegetable powders is shown. The technology of fruit and vegetable confectionery glaze with a high content of dietary fiber (9 g/100 g) and with a reduced amount of added sugar has been developed.

Effects of Adding Pectin to Milk in Varying Amounts on the Rheological Properties of Milk

Pectin, which is used as an additive in the food, cosmetics, pharmaceutical, and health sectors due to its safety, non-toxicity, low production cost, and high availability, is used as a thickener, gelling agent, brightener, stabilizer, emulsifier, and fat and sugar replacer in low-calorie foods. It is also used in milk and dairy products as a stabilizer to prevent proteins from clumping. In this study, the rheological properties of pectin and milk mixtures with pectin/milk powder (w/w) ratios of 0.1, 0.25, 0.5, 0.75, 1 and 1.5 were examined. First, a flow curve test was applied in the range of 0,01-1000 s-1 to obtain the viscosity curves and yield stress values of the samples. Then, an amplitude sweep test was performed at a fixed frequency of 10 rad/s and in the strain range of 0.01-100% to determine the linear viscoelastic range (LVR) of the samples and the solid and liquid structure of the samples. To determine the time-dependent behavior of the samples in non-destructive deformation, frequency sweep tests were performed at constant strain (0.01%) in the LVR range obtained from the amplitude sweep test and in the range of 0.1-100 rad/s. Finally, three interval thixotropy tests (3ITT) were performed to observe the structural recovery of the samples. As a result of rheological tests, it was determined that pectin-free milk showed Newtonian properties, other samples showed shear thinning properties, and viscosity values increased as the pectin rate increased. While all samples are solid at low strains, the liquid feature becomes dominant at high strains. It has been observed that as the pectin ratio in milk increases, the strain values at the yield point, where the liquid feature becomes dominant, also increase. Except for the sample with the highest pectin content, it was observed that the dominance of the storage modulus over the loss modulus was greater at low frequencies than at high frequencies. As a result of 3ITT, it was determined that the percentage of recovery at the 600th second increased as the pectin rate increased.

Microemulsion-Based Polymer Gels with Ketoprofen and Menthol: Physicochemical Properties and Drug Release Studies.

Ketoprofen is a non-steroidal, anti-inflammatory drug frequently incorporated in topical dosage forms which are an interesting alternatives for oral formulations. However, due to the physiological barrier function of skin, topical formulations may require some approaches to improve drug permeation across the skin. In this study, ketoprofen-loaded microemulsion-based gels with the addition of menthol, commonly known for absorption-enhancing activity in dermal products, were investigated. The main objective of this study was to analyze the physicochemical properties of the obtained gels in terms of topical application and to investigate the correlation between the gel composition and its mechanical properties and the drug release process. Microemulsion composition was selected with the use of a pseudoternary plot and the selected systems were tested for electrical conductivity, viscosity, pH, and particle diameter. The polymer gels obtained with Carbopol® EZ-3 were subjected to rheological and textural studies, as well as the drug release experiment. The obtained results indicate that the presence of ketoprofen slightly decreased yield stress values. A stronger effect was exerted by menthol presence, even though it was independent of menthol concentration. A similar tendency was seen for hardness and adhesiveness, as tested in texture profile analysis. Sample cohesiveness and the drug release rate were independent of the gel composition.

Investigating the Impact of Superabsorbent Polymer Sizes on Absorption and Cement Paste Rheology.

This study aims to understand the water retention capabilities of Superabsorbent Polymers (SAPs) in different alkaline environments for internal curing and to assess their impact on the rheological properties of cement paste. Therefore, the focus of this paper is on the absorption capacities of two different sizes of polyacrylic-based Superabsorbent Polymers : SAP A, with an average size of 28 µm, and SAP B, with an average size of 80 µm, in various solutions, such as pH 7, pH 11, pH 13, and cement filtrate solution (pH 13.73). Additionally, the study investigates the rheological properties of SAP-modified cement pastes, considering three different water-to-cement (w/c) ratios (0.4, 0.5, and 0.6) and four different dosages of SAPs (0.2%, 0.3%, 0.4%, and 0.5% by weight of cement). The results showed that the absorption capacity of SAP A was higher in all solutions compared to SAP B. However, both SAPs exhibited lower absorption capacity and early desorption in the cement filtrate solution. In contrast to the absorption results in pH 13 and cement filtrate solutions, the rheological properties, including plastic viscosity and yield stress, of the cement paste with a w/c ratio of 0.4 and 0.5, as well as both dry and wet (presoaked) SAPs, were higher than those of the cement paste without SAP, indicating continuous absorption by SAP. The viscosity and yield stress increased over time with increasing SAP dosage. However, in the mixes with a w/c ratio of 0.6, the values of plastic viscosity and yield stress were initially lower for the mixes with dry SAPs compared to the reference mix. Additionally, cement pastes containing wet SAP showed higher viscosity and yield stress compared to the pastes containing dry SAP.

Utilizing Euler poles for the evaluation of plate rigidity in numerical mantle convection models

SUMMARY Evidence that the Earth’s surface is divided into a tessellation of piece-wise rigidly translating plates is the primary observation supporting the solid-state creep-enabled convection paradigm, utilized to investigate evolution of the Earth’s mantle. Accordingly, identifying the system properties that allow for obtaining dynamically generated plates remains a primary objective in numerical global mantle convection simulations. The first challenge for analysing fluid dynamic model output for the generation of rigid plates is to identify candidate plate boundaries. Here, we utilize a previously introduced numerical tool for plate boundary detection which uses a user specified threshold (tolerance) to automatically detect candidate plate boundaries. The numerical tool is applied with different sensitivities, to investigate the nature of the surface velocity fields generated in three calculations described in earlier work. The cases examined differ by the values that they specify for the model yield stress, a parameter that can allow the formation of tightly focussed bands of surface deformation. The three calculations we examine include zones comprising possible plate boundaries that are characterized by convergence, divergence and strike-slip behaviour. Importance of the potential plate boundaries is assessed by examining the rigidity of the inferred model generated plates. The rigidity is measured by comparing the model velocities to the rigid rotation velocities implied by the statistically determined Euler poles for each candidate plate. We quantify a lack in rigidity by calculating a deformity field based on disagreement of actual surface velocity with rotation about the Euler pole. For intermediate yield stress and boundary detection threshold value, we find that the majority of the model surface can translate almost rigidly about distinct plate Euler poles. Regions that conform poorly to large-scale region rigid translation are also obtained but we find that generally these regions can be decomposed into subsets of smaller plates with a lower tolerance value. Alternatively, these regions may represent diffuse boundary zones. To clarify the degree to which the mantle convection model behaviour shows analogues with Earth’s current-day surface motion, we apply the plate boundary detection and Euler pole calculation methods to previously published terrestrial strain-rate data. Strong parallels are found in the response of the terrestrial data and mantle convection calculations to the threshold value, such that appropriate choice of that parameter results in very good agreement between observations and convection model character. We conclude that plates generated by fluid dynamic convection models can exhibit motion that is markedly rigid, and define statistics (plateness) and fields (deformity) by which the generation of self-consistently determined plate rigidity can be quantified, as well as describing how plate recognition might be optimized. We also note that in agreement with the Earth’s current state, we obtain a dozen dominant plates in the case exhibiting the most plate-like (rigid) surface, suggesting that this approximate number of plates is perhaps intrinsic to the geometry, surface area and physical properties of Earth’s mantle.

Flow properties of single origin chocolates: Effect of product formulation and particle size.

The objective of this research was to evaluate changes in flow behavior of chocolate during chocolate grinding using a stone grinder as affected by chocolate formulation. Three different types of chocolates were evaluated. Two chocolates without milk added (70% chocolate) and two chocolates with milk added and with different amounts of cocoa nibs (30% chocolate and 14% chocolate) were tested. For the 70% chocolates, nibs of two different origins were used; therefore, a total of four samples were evaluated. Chocolates were processed in a stone grinder, and samples were taken as a function of grinding time. For each timepoint, the flow behavior of the samples was measured using a rotational rheometer and fitted to the Casson model. Particle size was measured using a laser scattering instrument. Results showed that yield stress increased linearly while the Casson plastic viscosity decreased exponentially with grinding time (smaller particles). Particle size distribution of the chocolates showed a prominent bimodal distribution for short grinding times (∼9 h) with small (∼15 µm) and large (∼100 µm) particles; with longer grinding time, the population of larger particles decreased. Yield stress values were higher for the 70% chocolate, but they were not very different between the two milk chocolates tested. The Casson plastic viscosity was greatest for the 70% chocolate, followed by the 30% chocolate. The 14% chocolate had the lowest Casson plastic viscosity. Changes of Casson plastic viscosity with particle size were more evident for the dark chocolates compared to the milk ones. These results are helpful to small chocolate producers who need better understanding of how the formulation and grinding of chocolate affect its flow behavior, which will ultimately affect chocolate handling during production.

Advancing fracture toughness in high-strength TC18 alloy by optimizing the forging process

Optimizing performance and reducing costs often exhibit a trade-off relationship, thereby limiting the broader application of Ti alloys. To address the above challenge, this study involves comparative analyses of strength and fracture toughness, for TC18 alloy processed through distinct forging methods—long-period forging (M1) and short-period forging (M2). The results shows that both M1 and M2 present analogous content and dimensions of equiaxed primary α phase (αp) and secondary α phase (αs), as well as comparable values for yield stress (∼1050 MPa), and plasticity (∼7 %). Nevertheless, fracture toughness of the latter (M2) exhibits a notable increase (74.3 MPa∙m1/2) than that of the former (55.1 MPa∙m1/2). This phenomenon is primarily attributed to the heightened compatibility of mechanical properties and superior orientation relationship between αp and βt in M2 as opposed to M1. These characteristics give rise to a homogeneous deformation and an augmentation in void nucleation within the αp phase in the larger plastic deformation zone in M2. Additionally, the translocation of dislocations from αp/βt interfaces into the βt matrix in M2 is also verified by the tensile test at 3 % strain. The findings provide a promising insight for the design of low-cost Ti alloys with attractive strength and damage tolerance.

Influence of the thermal shrinkage-induced volume contraction on the yielding behavior of waxy oil

The present article investigates the effect of thermal shrinkage on the yielding behavior of waxy oil gel. The paper compares constant gap and constant normal force measurement protocols to examine the effect of measurement protocol on the rheological behavior of thermoreversible gel. The findings of this study reveal that the extent of stress overshoot and yield stress in a constant shear-rate start-up flow shows a lower magnitude in a constant gap protocol compared to a constant normal force protocol. The decrease in gel strength in the former protocol is mainly attributed to the formation of voids. These voids cause localized fractures within the crystal network. In contrast, in the constant normal force measurement protocol, gel contraction is compensated by utilizing a variable gap setting. Variable gaps compensate for the lower specific volume of the gel after crystallization, minimizing void formation and subsequent rupture of the crystal network. Hence, the gel network formed using the constant normal force protocol is more homogeneous, eliminating the uncertainties in yield stress measurement. Finally, the effect of thermal history, wax content, and aging period on the yield stress values highlights notable findings. Contrary to the conventionally accepted results, the aging period is found to impact the yield stress negatively, and a nonmonotonic relationship between the cooling rate and yield stress is noticed under the constant gap protocol. Thus, the results obtained under the constant normal force protocol are more reliable and can help in developing a fundamental understanding of the yielding behavior.

Tuning the rheological properties of chitosan/alginate hydrogels for tissue engineering application

Biomaterials that mimic biological tissues are in great demand in tissue engineering. Hydrogels are rising as a conducive candidate in tissue engineering on account of their water-holding capacity, mechanical strength, and elasticity. Nevertheless, the development of hydrogels that mimic biological tissues with the desired stability and mechanical strength, remains a notable barrier. In this investigation, chitosan/alginate hydrogels were prepared by tuning the chitosan concentration from 0.5 % to 2.5 %w/v with a fixed 1 %w/v alginate concentration using 0.1 % glutaraldehyde as a gelling agent. The hydrogel system forms through covalent bonding between chitosan and alginate, mediated by aldehyde groups of the glutaraldehyde. The mechanical strength of the hydrogel was elucidated by probing its viscoelastic behavior through rheological analysis. The rheological investigations revealed that the prepared chitosan/alginate hydrogels are profoundly stable with shear-thinning characteristics. The increase in chitosan concentration enhanced the stability and viscoelastic attributes of the hydrogels. The yield stress values ranging from 0.93 kPa to 14.24 kPa indicate the possibility of using these hydrogels in bioadhesives and soft and bone tissue engineering. The complex modulus of the prepared chitosan/alginate hydrogels resembles the shear modulus of liver tissues, osteogenic cells, and articular cartilage, and hence, these hydrogels pose as suitable candidates in liver, bone, and cartilage tissue engineering. The chitosan/alginate hydrogels possess outstanding self-healing ability, along with biocompatibility, stability, and mechanical strength, rendering them highly advantageous for applications in biomedical tissue engineering and bioadhesives.

Thermo-Mechanical Behavior and Strain Rate Sensitivity of 3D-Printed Polylactic Acid (PLA) below Glass Transition Temperature (Tg).

This study investigated the thermomechanical behavior of 4D-printed polylactic acid (PLA), focusing on its response to varying temperatures and strain rates in a wide range below the glass transition temperature (Tg). The material was characterized using tension, compression, and dynamic mechanical thermal analysis (DMTA), confirming PLA's strong dependency on strain rate and temperature. The glass transition temperature of 4D-printed PLA was determined to be 65 °C using a thermal analysis (DMTA). The elastic modulus changed from 1045.7 MPa in the glassy phase to 1.2 MPa in the rubber phase, showing the great shape memory potential of 4D-printed PLA. The filament tension tests revealed that the material's yield stress strongly depended on the strain rate at room temperature, with values ranging from 56 MPa to 43 MPA as the strain rate decreased. Using a commercial FDM Ultimaker printer, cylindrical compression samples were 3D-printed and then characterized under thermo-mechanical conditions. Thermo-mechanical compression tests were conducted at strain rates ranging from 0.0001 s-1 to 0.1 s-1 and at temperatures below the glass transition temperature (Tg) at 25, 37, and 50 °C. The conducted experimental tests showed that the material had distinct yield stress, strain softening, and strain hardening at very large deformations. Clear strain rate dependence was observed, particularly at quasi-static rates, with the temperature and strain rate significantly influencing PLA's mechanical properties, including yield stress. Yield stress values varied from 110 MPa at room temperature with a strain rate of 0.1 s-1 to 42 MPa at 50 °C with a strain rate of 0.0001 s-1. This study also included thermo-mechanical adiabatic tests, which revealed that higher strain rates of 0.01 s-1 and 0.1 s-1 led to self-heating due to non-dissipated generated heat. This internal heating caused additional softening at higher strain rates and lower stress values. Thermal imaging revealed temperature increases of 15 °C and 18 °C for strain rates of 0.01 s-1 and 0.1 s-1, respectively.

Emulsions, dipsticks and membranes based on oxalic acid-treated nanocellulose for the detection of aqueous and gaseous HgCl2

Although cellulosic materials have been used as stabilizing agents for oil-in-water emulsions since the 1980s, their properties and the underlying mechanism are not universal regardless of the dispersed phase or of the treatments on cellulose. One case of unconventional organic phase is acetic acid-containing chloroform, which is known to be a good solvent system for the preservation of dithizone. In turn, dithizone is a long-known chromogenic reagent for the colorimetric detection of HgCl2. However, its usefulness is limited by its fast degradation in polar solvents. For instance, its dissolution in ethanol and the subsequent impregnation of paper strips allowed to quantify aqueous HgCl2 reliably and quickly (5.4 – 27 mg L–1), but only if they were used along the first 24 h after dip coating. Furthermore, those strips could not be used for sublimated HgCl2. The dithizone/chloroform-in-water emulsions presented in this work overcame these limitations. We opted for oxalic acid-treated cellulose nanofibers (ox-CNFs) as stabilizer, aiming at a proper balance between amphiphilic character and electrostatic repulsion. In this sense, ox-CNFs attained good gel-forming ability with a low content of carboxylate groups. The minimum ox-CNF concentration required was 0.35 wt%, regardless of the proportion of chloroform. This consistency implied yield stress values above 0.7 Pa. Nanocellulose also provided film-forming capabilities, which were exploited to produce visually responsive dipsticks and membranes. While quantification and reproducibility were hampered by the increase in the complexity of the system, dithizone/ox-CNF films were still a valid option for HgCl2 detection, outperforming solution coating in terms of stability, blank signal, and selectivity.

Thixotropic chitosan hydrogels for biomedical applications: Unravelling the effect of chitosan concentration on the mechanical behaviour

Chitosan hydrogels are highly sought after in biomedical applications due to their biocompatibility, non-toxicity, and tunable mechanical properties. Nevertheless, achieving stable hydrogels with the required mechanical strength remains a notable obstacle. In this study, we prepared chitosan hydrogels with enhanced stability using minimal concentrations of glutaraldehyde to mitigate toxicity risks. The resulting hydrogel system is characterized by strong covalent bonds formed through imine and hydrogen bonding, facilitated by the aldehyde groups of glutaraldehyde. Rheological analyses reveal the viscoelastic properties of the hydrogels, showcasing stable gel-like structures with shear-thinning behavior, which are further enhanced with increasing chitosan concentration. Our observation demonstrates that the complex shear moduli of 0.5 - 1.5 w/v% chitosan hydrogel ranged between 3.08 kPa and 8.5 kPa, closely matching the shear moduli of the brain and connective tissues. The shear moduli obtained for the 2 w/v% (10.2 kPa) and 2.5 w/v% hydrogels (11.34 kPa) conform to the shear moduli of liver, fat, relaxed muscle, and breast gland tissue. Thixotropic studies reveal good structural recovery behaviour in the hydrogels. The swellability of 2 w/v% and 2.5 w/v% hydrogels (50–70 %) suggests their suitability for bone tissue engineering, with moderate porosity required for bone growth (60–75 %). Moreover, the yield stress values of 0.5 - 1.5 w/v% hydrogels satisfy the requirements for soft tissue engineering, while those of 2 and 2.5 w/v% match the requirements for bone tissue engineering. Our findings suggest that chitosan hydrogels of varying concentrations (0.5–2.5 % w/v) hold promise for a range of biomedical applications, including tissue engineering for brain, nerve, soft, and bone tissues, and wound dressing. This research addresses the pressing need for stable chitosan hydrogels with tailored mechanical properties, potentially offering solutions to challenges in biomedical materials design.