Search Results (201)

Driven by the rising frequency of extreme climatic events and the escalating demand for sustainable infrastructure, modern pavement materials must deliver enhanced resilience, structural stability, and environmental adaptability. This study presents the design and synthesis of a novel polyurethane-polyurea (PU-PUa) pavement binder, engineered via a synergistic framework combining nanoscale microphase separation and a hierarchical hydrogen-bonding network. Utilizing a streamlined, one-step synthesis approach involving an aliphatic isocyanate, a polyaspartic ester, polytetramethylene ether glycol, and 1,4-butanediol, the PU-PUa copolymer achieves distinct nanoscale phase separation between its hard and soft segments. Fourier transform infrared (FTIR) spectroscopy verifies the successful formation of characteristic PU-PUa moieties and a multi-scale hydrogen-bonding network, while DSC and DMA reveal SSC-dependent soft-segment mobility, crystallization/melting behavior, and viscoelastic relaxation. These intra- and inter-segmental interactions, together with thermally activated soft-segment transitions, establish the structural foundation for the macro-performance enhancement of the system. Comprehensive evaluations demonstrate that the PU-PUa binder exhibits excellent mechanical and highly tunable properties. Rheological measurements indicate that increasing the soft segment content (SSC) or incorporating an appropriate diluent concentration significantly lowers the system viscosity, thereby enhancing processing workability during mixing and paving. Contact angle goniometry reveals that the surface hydrophobicity of PU-PUa can be effectively regulated by adjusting the SSC, offering a viable strategy to optimize moisture damage resistance. Moreover, curing behavior analyses show that the polymerization kinetics are strictly governed by both the SSC and environmental temperature, where a lower SSC or elevated curing temperature accelerates strength development. Mechanically, the PU-PUa binder displays desirable surface hardness (>80 Shore A) and exceptional aggregate adhesion (>2 MPa), ensuring robust bonding stability and resistance to traffic-induced abrasion. Characterized by balanced tensile performance, the elongation at break of the binder can be tailored from 90% to 161%, while its tensile strength varies between 6.4 MPa and 17.8 MPa at intermediate temperatures, manifesting excellent resilience and cracking resistance. Overall, this molecular-to-macroscopic design strategy establishes the PU-PUa copolymer as a highly promising, durable binder for next-generation resilient pavement infrastructures. Full article

In recent years, the food industry has increasingly focused on reintegrating nutrient- and phytochemical-rich processing by-products into high-consumption food matrixes. Aligned with this trend, our study investigated melon peel powder (MPP) as a value-added, upcycled ingredient in biscuit formulations with 0, 5, 10, 15, and 20% (w/w) MPP as a partial replacement for wheat flour (WF). The effects of this substitution on nutritional profile, colour, physical properties, total phenolic content (TPC), total flavonoid content (TFC), DPPH radical scavenging activity, ferric reducing antioxidant power (FRAP), structural characteristics, and post-baking retention were evaluated. MPP exhibited higher TPC (1531.76 mg GAE/100 g DM), TFC (681.42 mg QE/100 g DM), FRAP (104.37 µM Fe²⁺/g DM) and DPPH (125.01 µM TE/g DM) than WF. Its incorporation improved nutritional quality by increasing dietary fiber and ash, while reducing available carbohydrates and energy value. Substantial enhancements were observed, with up to 6.72- and 6.93-fold increases in FRAP and DPPH, alongside 3.82- and 3.92-fold increases in TPC and TFC at the highest substitution level. Although baking reduced these levels, retention remained at 57–62% (TPC), 55–59% (TFC), 60–65% (FRAP), and 63–70% (DPPH), indicating partial thermal stability and possible contribution of heat-induced antioxidant compounds. MPP addition also affected technological properties, increasing baking yield and spread ratio while decreasing lightness (L*) and increasing yellowness (b*) and browning index (BI), resulting in yellow-brown tones. Fourier-transform infrared spectroscopy (FTIR) and wide-angle X-ray scattering (WAXS) analyses confirmed structural compatibility between WF and MPP, evidenced by the absence of new functional groups, preservation of the A-type crystalline structure of wheat starch without polymorphic transitions, and no indication of phase separation, whereas baking promoted starch gelatinization and integration of fibrous and pectic components. These findings support a potential valorisation pathway for melon by-products through their conversion into a value-added ingredient for biscuit production. Full article

Conventional water treatment relies on sequential flocculation and disinfection, which inflates infrastructure costs and heightens the risk of disinfection byproduct formation. Here, we report a magnetic lignin-based flocculant (LS-DMC-AM@Fe₃O₄) that integrates flocculation, sterilization, and rapid magnetic separation within a single material. The composite was synthesized by thermally initiated graft copolymerization of methacryloyloxyethyl trimethylammonium chloride (DMC) and acrylamide (AM) onto sodium lignosulfonate (LS), followed by incorporation of Fe₃O₄ nanoparticles (NPs) at 15 wt% loading; the product exhibited a saturation magnetization of 12.8 emu g⁻¹. LS-DMC-AM@Fe₃O₄ achieved 98.2% kaolin turbidity removal at 1 mg L⁻¹ and 98.6% E. coli removal at 8 mg L⁻¹, and displayed a markedly broader effective dosage window than its non-magnetic analog. We attribute this broadened window to Fe₃O₄-enhanced membrane disruption, which liberates anionic intracellular contents that buffer excess cationic charge and thereby suppress restabilization. The bactericidal efficiency reached 90% at 18 mg L⁻¹, 1.6-fold higher than LS-DMC-AM, governed by a synergistic dual mechanism: quaternary ammonium contact-killing coupled with Fe₃O₄ NP-induced intracellular reactive oxygen species (ROS) accumulation. Under an external magnetic field, flocs underwent rapid phase separation and displayed enhanced shear-regrowth capacity (E. coli floc recovery factor: 53% vs. 26%); Fe₃O₄ NPs were recovered at >95% efficiency over two cycles. Despite higher unit production costs, LS-DMC-AM@Fe₃O₄ delivers competitive per-unit-volume treatment economics through its ultralow effective dosage and magnetic seed recyclability. These results establish a viable strategy for engineering multifunctional, recyclable flocculants from industrial lignin waste. Full article

The remediation of contaminants of emerging concern (CECs) requires innovative, high-efficiency, and sustainable technologies. Here, we investigate active polymeric membranes incorporating TiO₂/ZnO heterojunctions for synergistic sono-enhanced photocatalytic water treatment under both UV and visible-light irradiation. TiO₂/ZnO composites were synthesized and characterized, confirming the formation of type II heterojunctions with tailored optical properties for sunlight-driven photocatalysis. The catalysts were integrated into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) matrixes using electrospinning (ES) and thermally induced phase separation (TIPS). ES membranes, specifically the ZnO-rich heterojunction within a PVDF-TrFE matrix (3T-7Z@TrFE ES), achieved the highest performance toward ciprofloxacin (CIP) degradation, reaching 71 and 57% under UV and visible light, respectively. The hybridization of the method by coupling ultrasound induced significant synergistic effects, with relative enhancement factors up to 1.38. Furthermore, the sono-enhanced photocatalytic pathway shifted the degradation mechanism towards the early fragmentation of the harmful piperazine ring, yielding a more sustainable degradation process. In addition, the composite membranes showed selective antibacterial activity against S. aureus, making this a multifunctional platform able not only to degrade CECs but also to mitigate membrane fouling. Overall, this work demonstrates the potential of tailored heterojunctions and composite membranes as sustainable platforms for the remediation of recalcitrant CECs in water, highlighting the synergy between photoactivity, piezoelectricity, and mechanistic control. Full article

Northern pike (Esox lucius) myofibrillar protein (MP) forms inherently weak gels due to endogenous proteolytic activity and the low thermal stability of fish myosin, limiting its application in surimi products. This study investigated the reinforcing effect and underlying mechanism of rice protein amyloid fibrils (RFs) on pike MP gels. Dynamic rheology revealed that RFs increased both the storage and loss moduli in a concentration-dependent manner, with the 5% group exhibiting an approximately threefold increase in the G′ at 100 rad/s relative to the control. The gel strength, hardness, and chewiness increased progressively with the RF content, whereas the water-holding capacity peaked at 1–3% RFs and declined sharply at 5% RFs. Microstructural imaging showed that moderate RF levels promoted a dense, homogeneous network architecture, while excessive RFs induced phase separation and structural heterogeneity. Hydrophobic interactions and hydrogen bonds were strengthened via RF incorporation, while disulfide bonds decreased monotonically with the increasing fibril concentration. FTIR spectroscopy revealed an α-helix-to-β-sheet transition, with the β-sheet content reaching a maximum of 49.37% at 3% RFs, and SDS-PAGE confirmed that the RF–MP interactions were predominantly non-covalent in nature. These results demonstrate that RFs reinforce pike MP gels through a molecular mechanism involving rigid fibrils acting as structural scaffolds within the protein network and a progressive shift from disulfide-mediated covalent crosslinking toward non-covalent stabilization via hydrophobic interactions and hydrogen bonding. The 1–3% RF range delivers the most balanced gel properties, while excessive fibril loading at 5% induces over-aggregation and impairs water retention. These findings establish amyloid fibrils as effective structural modifiers for freshwater fish gel products and provide a mechanistic basis for their application in surimi processing. Full article

Hybrid carbon nanotube–fullerene architectures provide a controllable setting in which to study irreversibility and information flow in strongly structured quantum environments. We analyze entropy generation in a platform where paramagnetic endohedral fullerenes (PEFs), such as N@C₆₀ and P@C₆₀, are encapsulated inside a suspended carbon nanotube (CNT) resonator, such that selected multi-level PEF spin states define an effective qubit coupled to quantized CNT flexural modes. Motivated by prior work on fullerene-filled CNTs, on spin–phonon manipulation in suspended nanotubes, and on exact phase-space propagators for damped driven oscillators, we formulate a hybrid open-system description that combines a driven quantum Brownian description of the CNT resonator with an effective Jaynes–Cummings type spin–vibrational interaction. The resonator dynamics are represented in phase space through the Wigner function, whose time evolution can be written analytically in terms of the initial Wigner distribution and a Gaussian propagator. This representation makes it possible to separate drive-induced phase space displacement, diffusion, and damping, and to connect these features directly to entropy flow. The coupled spin–mechanical dynamics are then embedded in a Lindblad quantum master equation that includes mechanical damping, spin relaxation, pure dephasing, and thermally activated excitation channels. Within this framework we derive the entropy balance equation—identifying entropy flux and non-negative entropy production—and examine how hybridization between the molecular spin and the nanotube vibration redistributes irreversibility between coherent exchange and dissipative channels. We show that spin–phonon coupling enhanced by a magnetic field gradient, resonant driving, and moderate thermal occupation can produce identifiable crossovers between entropy–production regimes dominated by the oscillator and those dominated by the spin. The resulting framework provides a quantitative basis for using CNT–PEF hybrids as nanoscale platforms for studying nonequilibrium quantum thermodynamics, decoherence, and information loss in structured vibrational environments. Full article

Developing membranes with superior antifouling properties is crucial for efficient and sustainable water treatment. In this study, polysulfone (PSM) composite membranes were fabricated by incorporating hydroxylated titanium nanotubes (TNT@OH) via the non-solvent-induced phase separation method. The hydroxylation of TNTs enhanced their dispersion in the polymer matrix and promoted strong polymer–nanoparticle interactions. Comprehensive characterization using FTIR, XRD, TGA, FESEM, and AFM confirmed the successful integration of TNT@OH, resulting in membranes with improved hydrophilicity, porosity, and thermal stability. The contact angle decreased from ~88° for neat PSM to ~50° at 7 wt% TNT@OH, while surface free energy increased significantly. Mechanical strength and flexibility were also enhanced at optimal TNT@OH loadings (3–5 wt%), owing to uniform dispersion and strong interfacial bonding. Filtration experiments using humic acid (HA) and natural organic matter (NOM) demonstrated remarkable improvements in water flux, rejection efficiency, and fouling resistance. The composite membranes achieved HA rejection rates of up to 98%, with reduced irreversible fouling and higher flux recovery ratios across multiple filtration–cleaning cycles. The proposed antifouling mechanism is attributed to the formation of a stable hydration layer by surface hydroxyl groups, which prevents foulant adhesion and facilitates cleaning. These findings suggest that incorporating TNT@OH into polysulfone membranes is a promising approach for developing high-performance ultrafiltration membranes with enhanced permeability, mechanical robustness, and long-term antifouling stability, thereby making them suitable for advanced water purification applications. Full article

The brittleness of bismaleimide (BMI) resin is a major issue that restricts its use as a matrix for advanced composites. Blending with thermoplastics constitutes an effective toughening approach that preserves the thermal resistance and mechanical properties of the resin. Reaction-induced phase separation is the primary toughening mechanism in thermoplastic-toughened BMI resin. However, the complex phase-separated structure causes the relationship between the glass transition temperature (T_g) and the curing degree to deviate from that described by the classical DiBenedetto equation. In this paper, two improved models, incorporating power-law correction and threshold inhibition, were constructed to address the phase-separation effect. An aerospace-grade BMI resin was toughened by a thermoplastic polyimide. The relationship between T_g and the curing degree was fitted by the DiBenedetto equation and the improved models. It was found that the adjusted coefficient of determination for the power-law correction and threshold inhibition models for the toughened resin increased to 0.978 and 0.995, respectively, whereas that of the DiBenedetto equation was only 0.612. This work provides a new, readily applicable empirical model for the prediction of T_g in thermoplastics-toughened thermosetting resins and offers theoretical support for optimizing the curing process and controlling the performance of multiphase resins. Full article

Perfluorosulfonic acid (PFSA) membranes, exemplified by Nafion, suffer dehydration-induced degradation at elevated temperatures, although modifications enhance their conductivity and performance. Sulfonated aromatic polymers (SAPs) exhibit weaker phase separation, yielding narrow, tortuous ion channels and lower conductivity than their PFSA membrane counterparts at equivalent ion exchange capacity; however, excessive sulfonation causes swelling and mechanical instability, offset by cost advantages. Phosphoric acid-doped polybenzimidazole (PBI) offers superior thermal stability and high conductivity, with recent advances in polybenzimidazole derivatives and composites driving medium-to-high temperature proton-exchange membrane fuel cell innovation. This review summarizes progress in three major medium-to-high temperature proton-exchange membrane fuel cell categories—perfluorosulfonic acid, sulfonated polymers, and PBI-based membranes—while addressing challenges and future goals for enhanced performance. Full article

Pressure fluctuations caused by a jet in crossflow (JICF) can induce cavitation and potentially damage wall surfaces. In mercury targets for a pulsed spallation neutron source, where cavitation damage progresses due to thermal shock, mercury is confined within a vessel that incorporates a double-wall structure—comprising a narrow channel and a main flow channel—to form parallel flows and suppress damage. However, as the damage progressed, penetration holes were formed in the inner wall separating these flows, and characteristic damage patterns were observed that suggest accelerated damage progression caused by JICF, in which a jet flows from the narrow channel into the main channel. The mechanism underlying this phenomenon has not been fully clarified. Therefore, the flow field and pressure fluctuations around the penetration hole were evaluated using PIV measurements in a water loop and numerical simulations of single-phase flow, with varying jet velocity and jet width. The results revealed that inflow through the penetration in the inner wall generates JICF, which produces vortices downstream of the inflow jet and induces pressure fluctuations that may be associated with cavitation. Full article

In this study, lithium was recovered from LiFePO₄ (LFP) cathode active materials through a two-step thermal process combining hydrogen reduction and chlorination roasting. Hydrogen reduction was conducted while varying temperature and holding time to promote oxygen removal from LFP and induce phase separation into Li₃PO₄ and iron phosphides (FeP and Fe₂P). Based on stoichiometric assessment using the degree of LFP decomposition and the reduction in oxygen moles, the optimal hydrogen-reduction condition was determined to be 900 °C for 1 h. Subsequently, CaCl₂ was selected as an appropriate chlorination agent using thermodynamic considerations, and the hydrogen-reduced product was reacted with CaCl₂ to convert Li₃PO₄ into water-soluble LiCl. The mass of LiCl produced was quantified as a function of reaction temperature. Water leaching enabled the separation of LiCl from the insoluble residues, resulting in an overall lithium recovery of 71.7%. Full article

Improving the interfacial compatibility between cellulose and poly(butylene adipate-co-terephthalate) (PBAT) is critical for enhancing the performance of PBAT-based composites. Here, microcrystalline cellulose (MCC) was homogeneously silanized at the molecular chain level using t-hexyldimethylchlorosilane (TDMS-Cl) as the modifier, yielding t-hexyldimethylsilylated cellulose (TDMS-Cell). TDMS-Cell/PBAT composite films were then prepared by solution blending and casting in tetrahydrofuran (THF). Structural characterizations confirmed the successful grafting of TDMS-Cl onto cellulose chains, resulting in TDMS-Cell with a degree of substitution of approximately 2. Microstructural observations combined with thermal analysis revealed that TDMS-Cell exerted a dual effect on the crystallization behavior of PBAT: it acted as a heterogeneous nucleating agent that increased the crystallization temperature, while the pronounced steric hindrance simultaneously suppressed crystal growth. Mechanical testing showed that simultaneous strengthening and toughening were achieved at an optimal TDMS-Cell loading of 3–5 wt%. Specifically, the tensile strength increased from ~16 MPa for neat PBAT to 21 MPa (31.25% improvement), and the elongation at break increased from ~700% to 964% (37.7% improvement). In addition, the incorporation of an appropriate amount of TDMS-Cell effectively enhanced the surface hydrophobicity of the composite films. At higher filler loading, however, solvent evaporation-induced phase separation led to self-aggregation of TDMS-Cell, which in turn deteriorated both the mechanical properties and surface hydrophobicity of the composites. Overall, this work systematically elucidates the structure–property relationships of silanized cellulose/PBAT composites in a homogeneous solution system, providing a rational basis for interfacial design and property optimization of PBAT/biomass-based composite materials. The prepared TDMS-Cell/PBAT composite films with balanced mechanical strength, tunable crystallization behavior, and improved surface hydrophobicity exhibit great potential for practical applications in high-performance flexible packaging materials, functional film substrates, lightweight composite structural components, and tunable hydrophobicity coating substrates. Full article

Sol–gel phase transitions are complex far-from-equilibrium processes characterized by limited reproducibility, whose origin remains poorly understood and rarely quantified. We investigated the thermally induced sol–gel transition of agar using turbidimetry. A phenomenological model was applied to extract key kinetic parameters (maximum absorbance, maximum rate, and characteristic times) from 96 independent replicates. Variability was quantified and compared with that of an enzymatic reaction exhibiting similar sigmoidal kinetics, allowing for separation of experimental, intrinsic, and nonergodic contributions. Agar gelation displays markedly higher variability. The total variability (CV ≈ 16%) exceeds both the experimental error (1–2%) and the nonergodic contribution (≈2%), demonstrating that it predominantly arises from intrinsic process dynamics. Variability increases sharply during early stages of gelation and then evolves more gradually, indicating that stochastic nucleation and network formation pathways drive divergent kinetic trajectories despite identical initial conditions. Variability in gelation is therefore not a measurement artifact but an intrinsic hallmark of the sol–gel transition. This inherent stochasticity limits the predictive power of deterministic models, particularly at meso- and microscopic scales, and should be considered a fundamental feature of gel-forming systems. Our approach provides a quantitative framework for characterizing variability in phase transitions and may be extended to more complex biological and soft matter systems. Full article

In this study, Ti-Co-Ce getter films were deposited via magnetron sputtering to investigate their activation mechanism—the thermal removal of surface passivation layers to restore gas sorption capability. The morphology before and after film activation was characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The oxygen content on the film surface before and after activation was measured using an energy-dispersive X-ray spectrometer (EDS), and gas desorption during activation was monitored with a quadrupole mass spectrometer (QMS). The combined results confirmed the absence of O₂ desorption during activation, suggesting oxygen migration into the film bulk. Crucially, in situ X-ray photoelectron spectroscopy (XPS) combined with controlled Ar⁺ ion sputtering depth profiling (0–30 nm) was employed to directly probe the chemical-state evolution within the thin film before and after thermal activation at 400 °C, thereby providing direct evidence of the activation dynamics. The data reveal that within the 0–10 nm near-surface region, a strong oxygen chemical potential gradient drives rapid oxide reduction and inward migration of lattice oxygen. At depths of 20–30 nm, moderate reduction coupled with oxygen enrichment induces phase separation, while around 30 nm, a dynamic equilibrium between oxygen inflow and outflow is established. These findings provide a theoretical basis for optimizing activation processes and guiding the development of low-temperature getter materials. This work is particularly relevant for MEMS, vacuum electronics, and other applications with stringent thermal budgets, expanding the design possibilities for heat-sensitive device integration. Full article

Laceration is one of the most common meniscus injuries, which can cause knee joint dysfunction. The treatment of meniscus injuries remains one of the greatest challenges in orthopedics. In this study, a three-dimensional sponge-like Poly(lactic acid)/Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (PLA/P(3HB-co-4HB)) scaffold with oriented microtubules was fabricated using an improved gradient thermal phase separation technique. The scaffold surface was modified by adsorbing gelatin. The surface-modified scaffolds and the unmodified scaffolds were divided into two groups. All preparation parameters were adjusted to meet tissue engineering requirements. The prepared scaffolds were tested for porosity, compression modulus, hydrophilicity, and degradability. Following scaffold preparation, induced differentiated rabbit bone marrow mesenchymal stem cells (BMSCs) were seeded to evaluate scaffold cytocompatibility. Cell proliferation was observed in the two scaffold groups, and cell viability was analyzed using CCK-8 assay, scanning electron microscopy (SEM), and confocal microscopy. Histological staining was performed to comparatively study cell synthetic function. Subsequently, tissue reconstruction and regeneration were evaluated following subcutaneous implantation of gelatin/PLA/P(3HB-co-4HB) scaffolds loaded with induced differentiated BMSCs in the dorsal regions of athymic nude mice. Results demonstrated that the gelatin/PLA/P(3HB-co-4HB) scaffold exhibited good cell compatibility, providing a suitable microenvironment for cell proliferation and differentiation. Furthermore, the scaffold supported the growth of seeded induced differentiated rabbit MSCs in vivo, maintaining meniscus cell phenotyping and function. The cell-laden scaffold has the potential to generate meniscus fibrocartilage. Full article