Rheology Modifiers Research Articles

Segmentation and Metallographic Evaluation of Aluminium Slurry Coatings Using Machine Learning Techniques

AbstractAnalysis of scanning electron microscope (SEM) images is crucial for characterising aluminide diffusion coatings deposited via the slurry route on steels, yet challenging due to various factors like imaging artefacts, noise, and overlapping features such as resin, precipitates, cracks, and pores. This study focuses on determining the thicknesses of the coating layers Fe2Al5 and, if present, FeAl, pore characteristics, and chromium precipitate fractions after the heat treatment that forms the diffusion coating. A deep learning SEM image segmentation model utilising U-Net architecture is proposed. Ground truth data were generated using the trainable Weka segmentation plugin in ImageJ, manually refined for accuracy, and supplemented with synthetic data from Blender 3D software for data augmentation of a limited number of SEM label images. The deep learning model trained on a combination of synthetic and real SEM data achieved mean dice scores of 98.7% ± 0.2 for the Fe2Al5 layer, 82.6% ± 8.1 for pores, and 81.48% ± 3.6 for precipitates when evaluated on manually labelled SEM data. The deep learning procedure was applied to evaluate a series of SEM images of diffusion coatings obtained with three different slurry compositions. The evaluation revealed that using a slurry without a rheology modifier may lead to a thicker partial Fe2Al5 layer that is formed by inward diffusion. The relation between the outward and inward diffusion Fe2Al5 layers was not affected by the coating thickness. The thinner diffusion coating presents lower pores and chromium precipitate fractions independently of the slurry selected.

3D Printable Polymeric Composite Material with Enhanced Conductivity Achieved by Affinity Matching.

Polymer-based conductive composites are lightweight, low-cost, and easily processable materials with important applications in various fields. However, achieving highly conductive and 3D printable polymer-based conductive composites remains challenging. In this study, we successfully developed a highly conductive composite suitable for direct ink writing 3D printing using unsaturated polyester resin as the polymer matrix and graphene nanosheets as conductive fillers and rheological modifiers. Due to the well-matched affinity between graphene nanosheets and unsaturated polyester, the graphene nanosheets aggregate within the unsaturated polyester, forming a 3D conductive network. Moreover, the shearing force during direct ink writing 3D printing induces the orientation of the 2D graphene nanosheets, significantly enhancing their conductivity along the printing direction. At room temperature, the unsaturated polyester resin/graphene composite shows a high conductivity of 69.9 S m-1 while maintaining excellent 3D printability. Structures printed using this material exhibit improved heat dissipation and electromagnetic shielding performance. The reported unsaturated polyester resin/graphene nanosheet composites demonstrate outstanding electrical and heat conductivity and excellent processability, making them promising candidates for applications in electromagnetic shielding, printed electronics, and other fields.

Bio-Templated Aerogel Fibers: Heterogeneous Spinodal Architecting and In Situ Fibrillation of Thermoplastic Polyurethane-Silica on Nanostructured Cellulose Nanofiber Scaffold for Enhanced Thermomechanical Performance.

This study addresses the inherent fragility and fractal limitations of traditional silica aerogels by developing a bio-templated aerogel fiber. Integrating cellulose nanofibers (CNFs), thermoplastic polyurethane (TPU), and silica aerogel (SA) in a dimethyl sulfoxide (DMSO) dispersion, a gel-spinning technique was employed to create aerogel fibers with superior thermomechanical performance. CNF also provided excellent rheological modification for successful spinnability, fast gelation, and fiber formation. The unique hierarchical structure of these fibers, formed through hot-stretching and surface modification, combined the superior mechanical strength and flexibility of TPU with the exceptional insulation properties of CNF and SA. The CNF network, encapsulated within the SA particles, formed a core-shell structure, axially aligned, that significantly enhances the thermal stability and mechanical performance of the fibers while maintaining a lightweight and porous architecture. Comprehensive morphological, thermal, and mechanical analyses were conducted to evaluate the properties of the developed aerogel fibers. Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy verified the successful surface modification and grafting reactions on CNF, contributing to improved hydrophobicity and thermal insulation. Adjusting the CNF content allowed for tailoring of the thermomechanical characteristics, with a notable 294% increase in tensile strength from 5.3 to 15.6 MPa and an enhanced crystallization temperature from 106 to 119.97 °C. Furthermore, cyclic tensile and compression tests validated the durability and shape recovery capabilities of the aerogel fibers, making them promising candidates for high-performance applications in extreme environments. The thermal conductivity validated by experimental data further highlights the potential of CNF-based aerogel fibers as sustainable and multifunctional materials for advanced thermal insulation, mechanical reinforcement, and flexible structural applications.

Carboxymethylcellulose–laponite nanocomposites as a temperature-resistant rheological modifier

Carboxymethylcellulose–laponite nanocomposites as a temperature-resistant rheological modifier

Thermosensitive polymer/nanosilica hybrid as a multifunctional additive in water-based drilling fluid: rheologicalproperties and lubrication performance as well as filtration loss reduction capacity

In previous studies, for obtaining a flat rheological drilling fluid, binary and ternary thermosensitive silica (SiO2) nanohybrids as rheological modifiers were synthesized using N-isopropylacrylamide with a thermal association temperatureof 32-33 oC as the thermosensitive monomer [J. Petrol. Sci. Eng. 219 (2022), 111096; Geoenergy Science and Engineering 228 (2023), 211934]. However, the as-synthesized SiO2 nanohybrids exhibited limited performance and low thermal transition temperature. Thus surface initiated atom transfer radical polymerization was utilized to graft hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) onto SiO2 surface to obtain PEGMA/SiO2 nanohybrids with an elevated thermal association temperature of 75°C. The morphology and structure of the as-synthesized PEGMA/SiO2nanohybrid were characterized by infrared spectroscopy and transmission electron microscopy; and its effects as a thermosensitive multifunctional additive on the rheological properties and lubrication performance as well as filtration loss reduction capacity of a water-based drilling fluid were investigated. Results indicate that the drilling fluids with 1.0% PEGMA/SiO2 nanohybrids exhibited obvious thermal thickening behavior in the temperature range of 70-80 °C; at low temperatures, however, they had a significant viscosity reduction effect therein. At room temperature, the apparent viscosity and plastic viscosity were reduced by 68% and 50%, respectively. Besides, due to the tightly packed plugging layer formed by PEGMA/SiO2 nanohybrids and bentonite, the filtration loss of the drilling fluids containing 1.0% PEGMA/SiO2 nanohybrid was reduced by 37% as compared with that of the base slurry; and the lubrication coefficient was decreased by up to 50%. Moreover, the high-temperature aging process promoted the intermolecular interactions of the nanohybrids and their interaction with bentonite flakes, thereby further improving the rheological behavior, filtration reduction ability, and lubricity of the drilling fluids. The as-synthesized thermosensitive PEGMA/SiO2 nanohybrids with excellent multifunctionality could find promising application in water-based drilling fluids.

Effect of CO2 mixing on the rheological and electrochemical properties of fresh mortar at the early age

The study aimed to elucidate the mechanism behind rheological modification due to CO2 mixing at the mixing and post-mixing stages from an electrochemical perspective. The results indicated that CO2 mixing reduced the flowability while increasing penetration resistance and static yield stress. The electrostatic attraction between particles with opposite surface charges and the bridging effect of calcium carbonate constitute the primary factors for influencing the rheological properties of mortar at an early age. The altered surface charge of carbonized cement particles, primarily resulting from CO2 injection lowering the pH and ion concentration, reversed the zeta potential of particles from the traditionally negative charge (-3.59 mV) to a positive value (+13.3 mV). Furthermore, CO2 mixing further enhanced the dissolution of cement particles and accelerated the hydration process, thereby increasing the rate of structural build-up. CO2 mixing was demonstrated to be a potential rheological modifier for 3D-printed concrete applications.

The effect of graphene properties on the extrusion of a shape memory epoxy vitrimer

Thermoset polymers exhibit very appealing mechanical and functional properties. Direct ink writing (DIW) could open new possibilities in the design and fabrication of intricate thermoset parts, but it often requires the use of additives such as fumed silica or nanoclays to modify the rheology of uncured epoxies. However, relatively large concentrations are usually needed what can be detrimental to properties. Graphene-derived additives are an appealing alternative, but we need to understand the key physicochemical characteristics that define an optimum graphene rheology modifier. Here we compare the effect of three different carbon fillers on the viscoelastic response of a reprocessable epoxy vitrimer with shape memory capabilities, graphene oxide (GO), reduced graphene oxide (rGO), and graphene powder (GP), and assess the effect of their chemistry and morphology. The analysis shows that large (∼20 μm in size) rGO flakes enable the formation of strong, printable gels, through Van der Waals interactions and physical entanglement. The vitrimer could be successfully printed by incorporating 5 wt% of rGO. The printed parts exhibit tensile strengths (30–60 MPa), moduli (2–3 GPa), strength recovery after reprocessing (∼80 %), shape-memory properties comparable to the pure epoxy, and improved water resistance due to the introduction of hydrophobic rGO.

An investigation of rheological properties and sustainability of various 3D printing concrete mixtures with alternative binders and rheological modifiers

This study assessed the performance of eco-friendly 3D printable mixtures prepared with various wastes such as fly ash (FA), granulated blast furnace slag, and marble dust. Additionally, the study investigated the impact of a viscosity-modifying agent (VMA) and silica fume (SF) on the mixtures’ rheological and mechanical characteristics. The influence of different wastes and VMAs on the fresh and hardened properties of printable mixes was investigated. Besides, the extrudability and buildability properties of the mixtures were evaluated with a manual extrusion device. The sustainability assessment was conducted using embodied CO2 and embodied energy index, integrating both the mixtures’ environmental implications and engineering characteristics. Experimental outcomes indicated that the inclusion of SF led to enhancements in the fresh properties of the 3D printable mixes. The VMA mixes exhibited significantly higher static yield strength than mixes incorporating SF. Considering printability and sustainability, the FA-SF mixture was identified as the optimal one.

Evaluation of basalt fibers and nanoclays to enhance extrudability and buildability of 3D-printing mortars

A study of the rheological and fresh mechanical properties of fly ash-cement 3D printing (3DP) mortars with six types of nanoclays (NC) as rheology modifiers, two sepiolites, three attapulgites and one bentonite, and reinforced with short basalt fibers (BF) was carried out. Fresh mortar properties were evaluated with a flow table test (FTT), cylindrical slump test (CST) and cone-penetration test (CPT) on samples left at rest and stirred before testing. Squeeze test (SQT) was carried out on samples cast-in-the-mold and 3D printed to compare the effects of 3DP on the fresh mechanical behavior. Extrudability was assessed with an electrical barrel extrusion device. NC and BF enhanced mortar cohesion by preventing water drainage and improving material extrudability. NC increased shear yield stress (τ0) over time on samples left at rest, enhancing reversible thixotropy. Besides, NC required larger amounts of superplasticizer, increasing open time windows. Among NC, Sepiolite in powder form showed the best fresh mechanical performance on 3DP samples. BF enhanced extrudability due to the bridging effect but also shows mechanical synergies with some NC. 3DP samples showed lower compressive yield stress and Young modulus evolution over time (σ˙ and Ė) than cast-in-the-mold samples, due to their layered structure.

Bottlebrush Midblocks Promote Colloidal Bridging of Telechelic Polymers.

Telechelic polymers are effective rheological modifiers that bridge between associative constituents to form elastic networks. The performance of linear telechelic chains, however, is controlled by entropic forces and thus suffers from an upper limit on bridge formation. This work overcomes this limitation by utilizing telechelic triblock copolymers containing bottlebrush midblocks. By comparing the rheological properties of emulsions linked by telechelic bottlebrush polymers to those containing linear chains, we determined that telechelic polymers with bottlebrush midblocks form elastic networks more efficiently. These enhanced rheological properties arise from the high stiffness of the bottlebrush midblocks, which offsets the entropic stretching penalty for bridge formation, enabling them to more readily form networks. This molecular-level control over polymer conformation in complex fluids opens avenues for designing highly elastic networks with minimal polymeric additives.

Influence of Rheological Modifications on Primary Network Chemical and Structural Cure Kinetics for an Interpenetrating Polymer Network Resin.

The development of non-contact in situ techniques for monitoring cure kinetics has the potential to greatly improve both resin formulation and processing. We have recently shown that low-frequency Raman spectroscopy is a viable method for assessing resin structural cure kinetics and complements the traditional chemical conversion determined from the fingerprint region of the spectrum. In this work, we further evaluate the relationship between structural and chemical conversion by investigating two chemically identical yet rheologically different interpenetrating polymer network resin formulations. Rheological analysis demonstrates a relationship between structural conversion and storage modulus, which is not observed in the chemical conversion data. We show that one can produce master cure kinetics curves with comparable kinetic constants using both the chemical and structural conversion methodologies. Parametric analysis of the structural conversion, chemical conversion, and photorheological conversion was combined with a semi-empirical model for the storage shear modulus as a function of the extent of cure.

Rheology modification in a subduction channel due to eclogite facies metasomatism (Rocky Beach Metamorphic Mélange, Port Macquarie, Australia)

The rheological properties of the interface between the down-going and overriding plates in subduction zones provides insight into how plate convergence is accommodated and the controls on seismic and aseismic slip. This interface is known as the subduction channel and exhumed examples provide the only direct information on deformation mechanisms and the impact of metamorphism on rheology. The Rocky Beach Metamorphic Mélange in eastern Australia is one such exhumed subduction channel, composed of eclogite, blueschist and greenschist facies blocks within a mélange matrix. Previous phase equilibria modelling indicates that high pressure blocks were subducted to ca. 100 km depth and then retrogressed during return flow and exhumation. We found that the rheology of blocks is modified by metasomatism, consistent with studies on other subduction channels. However, through comparison of blocks from different metamorphic grades we found that the effect of metasomatism on rheology varied depending on the pressure and temperature conditions of metasomatism. While unmetasomatised eclogites behaved as rigid objects in the mélange matrix, rocks with mineral assemblages that equilibrated during eclogite facies metasomatism accumulated significant strain, forming isoclinal folds and refolded folds. Deformation of these blocks began at eclogite facies and continued during return flow and retrogression to blueschist facies. At blueschist facies, metasomatised blocks developed mm-scale isoclinal folds with shearing parallel to fold limbs forming rootless isoclinal folds. At the transition between blueschist and greenschist facies, pressure solution became important, preferentially focusing along layers of lawsonite, dissolving it from the rock. At greenschist facies, dissolution-precipitation processes caused significant mass loss, producing mm-spacing between pressure solution seams and cuspate folds, analogous to dewatering structures in sediments. In the Rocky Beach Metamorphic Mélange eclogite facies metasomatism reduces the competence of rigid blocks, reducing overall subduction channel heterogeneity during return flow. We suggest that subduction channels that experience widespread eclogite facies metasomatism may be less likely to generate seismic slip during return flow, since the proportion of rigid blocks and block strength are both reduced.

Exopolysaccharides as bio-based rheology modifiers from microalgae produced on dairy industry waste: Towards a circular bioeconomy approach

The feasibility of exopolysaccharides (EPS) production from cheese whey using Chlorella vulgaris was investigated as an example of circular bioeconomy application. The effects of dairy waste utilization in EPS biosynthesis and rheological properties were evaluated, comparing with both control conditions and commercial xanthan gum (CXG). A twofold increase in yield, up to 0.32 g L−1, was observed when Chlorella vulgaris was used for EPS production from whey rather than conventional fertilizers. Additionally, the EPS produced using cheese whey exhibited superior pseudoplasticity in the 0.4–1.0 (w/v) range compared to the control. The EPS from the whey wastewater contained functional groups similar to those of CXG (82.7 %). Moreover, the solutions containing 1 % biopolymer showed rheological profiles similar to those of the 0.4 % CXG. The molecular weight averages predominantly fell within the range of 284 to 324 kDa, as deduced using diffusion NMR, an innovative and rapid determination method for estimating EPS size. The potential applications of EPS notably extend beyond the dairy industry, reaching diverse market sectors, and thereby enhancing the competitiveness of microalgal biorefineries while contributing to the achievement of Sustainable Development Goals.

Enhancing the performance of 3D-printed fiber-Reinforced mortar: synergistic effects of clays and bacterial cells as viscosity modifying agents

The absence of standardized 3D concrete printing mixtures drives ongoing material exploration. This study investigates mineral and bio-based viscosity modifying agents (VMAs) application in fiber-reinforced cementitious mortar. Nano-montmorillonite, sepiolite, and bacterial cells function as supplementary materials, partially substituting cement with fly ash for sustainability assessment and compatibility evaluation in our study. Mechanical tests encompass compressive, flexural strength, and interlayer bonding in 3D-printed samples. Based on the results, incorporating 0.150% Polyamide (PA) fiber positively affected interlayer bonding strength and deceleration of the flow loss rate. Additionally, adding clays decreased workability and compressive strength but improved interlayer bonding and flexural properties. On the other hand, substituting 20% of cement with FA improved the flowability of the mixture and showed great compatibility with other materials during printing. Applying a cement paste layer was evaluated as a practical method for bond enhancement at the interface. Bacteria incorporation improved flexural strength but weakened interlayer bonding. However, the combination of bacteria and clays resulted in a superior improvement in mechanical properties. This study demonstrates clays and bacteria’s potential in enhancing rheological and mechanical features in cementitious fiber-reinforced mortar. Notably, this study introduces bacteria cells and sepiolite as rheology modifiers in 3D concrete printing for the first time. Additionally, it presents a novel dog-bone-shaped structure test for assessing interlayer bond performance.

Brazilian Requeijão “soft cheese” with added microparticulated whey proteins: rheological modifications

Brazilian Requeijão “soft cheese” with added microparticulated whey proteins: rheological modifications

Biobased Self-Healing Thin Film Coatings Based on Poly (Itaconic Acid Esters).

Paper used for packaging applications is often coated with thin polymer coatings to improve the properties, like printability and barrier properties, respectively. Today, these coatings are still often based on petroleum-based polymers. In this study, the fabrication of biobased thin film coatings is described. Poly(itaconic acid ester)s, which are prepared by emulsion polymerization, are used as water-based coatings for paper. The thermal properties of the polymers are tuned by the side chain of the monomers (diethyl itaconate vs. dibutyl itaconate). Different formulations based on the polymer emulsion and additives, like rheology modifiers, are prepared and their film formation is studied. The usage of a rheology modifier results in excellent film formation. These polymer coatings feature an additional function - they are capable of self-healing. The healing ability is studied in scratch healing tests, in which almost complete recovery can be observed after healing at 100 °C. Moreover, the restoration of optical properties/aesthetics is studied. In gloss measurements before and after damage as well as after a healing time the complete recovery of the gloss can be observed. Furthermore, the barrier properties against fat are studied.

Nanocrystalline Cellulose to Reduce Superplasticizer Demand in 3D Printing of Cementitious Materials.

One challenge for 3D printing is that the mortar must flow easily through the printer nozzle, and after printing, it must develop compressive strength fast and high enough to support the layers on it. This requires an exact and difficult control of the superplasticizer (SP) dosing. Nanocrystalline cellulose (CNC) has gained significant interest as a rheological modifier of mortar by interacting with the various cement components. This research studied the potential of nanocrystalline cellulose (CNC) as a mortar aid for 3D printing and its interactions with SPs. Interactions of a CNC and SP with cement suspensions were investigated by means of monitoring the effect on cement dispersion (by monitoring the particle chord length distributions in real time) and their impact on mortar mechanical properties. Although cement dispersion was increased by both CNC and SP, only CNC prevented cement agglomeration when shearing was reduced. Furthermore, combining SP and CNC led to faster development of compressive strength and increased compressive strength up to 30% compared to mortar that had undergone a one-day curing process.

Characterization of temperature regulating, high-temperature rheological and anti-aging properties of asphalt mastic modified with SSPCMs

The objective of this study is to explore the potential of utilizing self-developed SSPCMs as additives for heat storage temperature regulation in asphalt mastic modification. To achieve this aim, a variety of asphalt mastics with different F-A volume ratios and SSPCM contents were formulated, and their high-temperature rheological properties, modification mechanisms, thermoregulation capabilities, and aging resistance performances were analyzed. The results of temperature regulation test indicated that the maximum cooling amplitude of asphalt mastic could reach 11.3°C, showing a great promising application for cooling asphalt pavements. Additionally, the incorporation of SSPCMs generally resulted in positive impacts on both the high-temperature rheological properties and temperature sensitivity of the asphalt mastics. Moreover, the aging indices GAI, ICO and ISO of the modified asphalt mastic with 30 % SSPCMs decreased by 5.6 %, 18.3 % and 8.7 %, respectively, compared with control asphalt mastic, implying that the incorporation of SSPCMs can retard the aging process of asphalt and enhance the thermal oxidative aging resistance of the asphalt mastics. In summary, the current study demonstrates the feasibility, improved performance, and effective thermoregulation properties of SSPCMs in asphalt mastics.

Sequence and gelation in supramolecular polymers.

Supramolecular polymer networks exhibit unique and tunable thermodynamic and dynamic properties that are attractive for a wide array of applications, such as adhesives, rheology modifiers, and compatibilizers. Coherent states (CS) field theories have emerged as a powerful approach for describing the possibly infinite reaction products that result from associating polymers. Up to this point, CS theories have focused on relatively simple polymer architectures. In this work, we develop an extension of the CS framework to study polymers with reversible bonds distributed along the polymer backbone, opening a broad array of new materials that can be studied with theoretical methods. We use this framework to discern the role of reactive site placement on sol-gel phase behavior, including the prediction of a microstructured gel phase that has not been reported for neutral polymer gels. Our results highlight the subtleties of thermodynamics in supramolecular polymers and the necessity for theories that capture them.

A Scalable and Surfactant-Free Emulsion Method for Producing Microbeads from Varied Biomass Feedstocks.

Despite national and international regulations, plastic microbeads are still widely used in personal care and consumer products (PCCPs). These exfoliants and rheological modifiers cause significant microplastic pollution in natural aquatic environments. Microbeads from nonderivatized biomass like cellulose and lignin can offer a sustainable alternative to these nondegradable microplastics, but processing this biomass into microbeads is challenging due to limited viable solvents and high biomass solution viscosities. To produce biomass microbeads of the appropriate size range for PCCPs (ca. 200-800 μm diameter) with shapes and mechanical properties comparable to those of commercial plastic microbeads, we used a surfactant-free emulsion/precipitation method, mixing biomass solutions in 1-ethyl-3-methylimidazolium acetate (EMImAc) with various oils and precipitating with ethanol. While yield of microbeads within the target size range highly depends on purification conditions, optimized protocols led to >90% yield of cellulose microbeads. Kraft lignin was then successfully incorporated into beads at up to 20 wt %; however, higher lignin contents result in emulsion destabilization unless surfactant is added. Finally, the microbead shape and surface morphology can be tuned using oils of varying viscosities and interfacial tensions. Dripping measurements and pendant drop tensiometry confirmed that the higher affinity of cellulose for certain oil/IL interfaces largely controlled the observed surface morphology. This work thus outlines how biomass composition, oil viscosity, and interfacial properties can be altered to produce more sustainable microbeads for use in PCCPs, which have desirable mechanical properties and can be produced over a wide range of shapes and surface morphologies.