Search Results (884)

The textile industry faces significant challenges regarding the need for textile waste recycling. This study investigates the feasibility of alkaline hydrolysis assisted by alcoholic co-solvents, such as ethanol, for recycling polyester/cotton blend textiles. Ethanol-assisted alkaline hydrolysis under mild conditions enabled almost complete depolymerisation of polyester, allowing the recovery of its monomers, terephthalic acid and ethylene glycol, which may be used to produce new polyester fibre. However, the treatment was found to adversely affect the properties of the cotton fibres, resulting in a recycled material of lower quality and functionality than the original material. In particular, a significant change in the structure of the cotton fibre was observed, namely, the transformation of cellulose I into cellulose II, as confirmed by FTIR analysis, along with a decrease in both the degree of polymerization and tensile strength, especially at an ethanol/water ratio of 40/60. Hence, alcohol-assisted alkaline hydrolysis is advisable for the chemical recycling of polyester, but it presents limitations when cotton fibres are also present. Full article

Polymeric microspheres synthesized via Pickering emulsion polymerization offer structural tunability, making them attractive platforms for dye adsorption. This study investigates the adsorption behavior of methylene blue onto two classes of polymeric microspheres—poly(methacrylic acid) crosslinked with ethylene glycol dimethacrylate (PM), containing both micro- and nanopores, and poly(methacrylic acid) crosslinked with divinylbenzene (PD), containing only nanopores. The adsorption kinetics were modeled using a dual-process approach that distinguishes between diffusion-controlled transport and surface-controlled kinetic adsorption. We quantified the relative contributions of these mechanisms and correlated them with particle architecture. In the PM particles, diffusion plays a significant role in smaller particles with larger macropores, enabling methylene blue to penetrate the interior. As the particle size increased and macroporosity decreased, adsorption becomes increasingly dominated by surface kinetics. In contrast, PD particles —which lack macropores—showed the opposite trend: smaller particles were primarily governed by fast surface adsorption, while in larger particles, diffusion through nanopores became increasingly relevant. Correlation analysis between adsorption rate constants and structural parameters such as particle diameter and pore sizes revealed strong, opposing trends. In PD particles, a near-perfect inverse correlation was observed between the diffusion and kinetic components, indicating competitive suppression, where the dominance of one mechanism limited the contribution of the other. These results demonstrated that internal pore architecture played a central role in controlling the adsorption mechanism. Tuning particle size and porosity allowed deliberate control over the balance between diffusion and surface kinetics, enabling the rational design of microparticle adsorbents with tailored uptake behavior for water purification and dye removal applications. Full article

Polylactide (PLA) has become widely adopted across biomedical, packaging, and manufacturing sectors due to its biodegradability and renewable sourcing. However, the rapid growth in PLA consumption has created urgent challenges related to waste management and the cleaning of processing equipment. This study investigates glycolysis as a promising chemical depolymerization pathway for PLA recycling and in situ reactor cleaning. A systematic analysis of four glycolysis agents (GA) (ethylene glycol, diethylene glycol, propylene glycol, and glycerol) was performed across molar PLA:GA ratios from 1:0.125 to 1:4 at 220 °C, targeting the efficient conversion of high-molecular-weight PLA (Mn ≈ 165 kDa) into low-molecular-weight oligomers. Gel permeation chromatography (GPC) demonstrated that propylene glycol exhibited the highest depolymerization efficiency, yielding oligomers with Mn as low as 200 g·mol⁻¹ even at minimal glycolysis agent ratios, while glycerol produced hydroxyl-rich oligomers optimal for subsequent lactide synthesis. Hydroxyl value (HV) measurements showed excellent agreement with theoretical values (<5% deviation), allowing us to make an assumption about an approximate, close to near-quantitative con-version. Glycolysis products with Mw below 400 g·mol⁻¹ displayed excellent water solubility, making them particularly attractive for reactor cleaning applications. Using glycerol-derived (GL) oligomers (PLA:GL = 1:0.25), purified L-lactide with a melting point of 98.1 °C and high purity (>99%) was obtained through thermocatalytic depolymerization and five recrystallization cycles, as confirmed by ¹H nuclear magnetic resonance (¹H NMR) and differential scanning calorimetry (DSC) analyses. The recovered lactide’s high purity renders it suitable for ring-opening polymerization, enabling closed-loop PLA recycling schemes. Overall, glycolysis emerges as a highly promising chemical recycling route complementary to hydrolysis and pyrolysis: propylene glycol maximizes depolymerization efficiency for cleaning applications, while glycerol optimizes oligomer functionality for lactide recovery and advanced material synthesis. Our results provide practical guidelines for selecting glycolysis agents and conditions for cleaning and recycling applications. Full article

In addition to the inherent challenges associated with controlling polymerization reactors, the “Sclairtech” technology for the production of Linear Low-Density PolyEthylene (LLDPE) presents specific characteristics (e.g., high temperature and pressure and a residence time in the reactor of less than 1 min) which add further difficulties to the effective control of the main quality parameters of the polymer produced. This work presents a strategy for implementing advanced control in a real LLDPE production unit (“Sclairtech” technology) followed by a systematic evaluation of the economic benefits in accordance with best international practices. Melt Index (MI), density and conversion were considered as controlled variables. The methodology for implementing advanced control involved analysis by resin classes (rotational molding, low-density injection, octene film and high-density injection) and effective contributions such as an innovative strategy for reactor temperature control. The proposed control strategy is capable of efficiently addressing two of the main problems associated with “Sclairtech” technology, namely, the generation of out-of-specification product during grade transitions and wide specification ranges. The benefits analysis involved the use of real process data, a statistical analysis of key variables to identify the dispersion and percentage of out-of-specification products, and the calculation of the net present value of financial indicators capable of validating the investment. Regarding quantitative outcomes, an annual gain of US$ 791,812 was estimated, with US$ 494,883 coming from the reduction in catalyst consumption and US$ 296,929 from other sources (reduction in out-of-specification product and production losses associated with grade transitions). Full article

Development of new polymers that cannot be achieved by using conventional catalysts has been the central research objective, and copolymerization is an effective strategy to modify the materials’ (thermal, physical, mechanical and electronic) properties. Modified half-titanocenes, Cp’TiX₂(Y) (Cp’ = cyclopentadienyl, X = Cl, Me, etc, Y = anionic donor such as phenoxide, ketimide, amidinate, etc.), are known to be effective catalysts. This review introduces several selected efforts for efficient synthesis of ethylene copolymers containing cyclic olefins, biobased conjugated dienes, and disubstituted α-olefins, including the effect of cocatalysts. Moreover, here we introduce an analysis using XAS (X-ray absorption spectroscopy), which has been recognized as a powerful method providing direct information on the catalytically active species, such as coordination numbers and the distances of the coordinated atoms as well as oxidation state and the geometry of the metal centre in catalyst solution. Full article

In recent years, sustainability and the concept of a circular economy have grown in importance within almost all industrial sectors. Especially in the chemical industry, recycling of polymer waste streams has become an important pathway to avoid plastic waste being landfilled or incinerated. Additionally, traditional carbon sources, such as fossil fuels, can be substituted with streams of recycled polymer. For example, polyethylene terephthalate (PET), which is utilized in plastic bottles and textiles, may be recycled via glycolysis. This depolymerization yields the monomer bis(2-hydroxyethyl) terephthalate (BHET). This study focuses on the thermal behavior and stability of BHET, both in pure form as well as in the presence of ethylene glycol (EG), as it results from PET glycolysis. For this, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), high-performance liquid chromatography (HPLC), powder X-ray diffraction (PXRD), and thermogravimetry (TG) were utilized. The results exhibited pure BHET polymerizing to PET at temperatures above 120 °C, while further increasing temperatures increased the reaction kinetics. Additionally, no reaction was observed in BHET/EG mixtures at any temperature investigated, which can be attributed to the presence of EG shifting the equilibrium of the reaction towards the BHET, thus inhibiting polymerization. Based on these results and the determined BHET/EG (solubility) phase diagram, potential purification strategies based on crystallization are proposed. Full article

Poly(ethylene terephthalate) (PET) is a widely used commodity polymer owing to its low cost, excellent mechanical properties, and high processability. Chemical modification of PET surfaces to impart specific functionalities represents an effective strategy for transforming PET into high-value-added materials without altering its bulk properties. In this study, we investigated the surface functionalization of PET substrates using surface-initiated atom transfer radical polymerization (SI-ATRP). ATRP initiation sites were introduced onto PET surfaces through mild surface hydrolysis followed by polyethyleneimine coating. To further enhance the grafting density, an inimer-based strategy was employed, in which a bifunctional monomer containing both a polymerizable group and a latent initiation site was used to form hyperbranched polymer structures on the PET surface, thereby amplifying the number of active initiation sites. Using these modified PET substrates, SI-ATRP of functional methacrylate monomers was successfully carried out. Grafting of poly(2,2,2-trifluoroethyl methacrylate) imparted highly hydrophobic surface properties, yielding water contact angles above 120°, whereas grafting of poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride) produced hydrophilic surfaces with contact angles below 20°. Surface characterization by X-ray photoelectron spectroscopy confirmed successful graft polymerization and effective surface coverage. While the macroscopic wettability was primarily governed by the chemical nature of the grafted polymers, the inimer-based initiation-site amplification significantly enhanced the surface electrostatic properties of the polycationic polymer–grafted surfaces, increasing the ζ-potential from approximately +20 mV to over +100 mV. Antibacterial tests using Escherichia coli K-12 as a model bacterium demonstrated that PET substrates grafted with poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride) exhibited clear contact-active antibacterial activity, achieving up to 2-log reduction in viable bacterial counts after 3 h of contact incubation. These results highlight the importance of molecular-level control of grafting architecture and surface electrostatic properties in the design of functional antibacterial PET surfaces. Full article

Temperature regulation of gas-phase ethylene polymerization fluidized bed reactors (FBRs) is challenging due to strong nonlinearities, highly exothermic reaction kinetics, and frequent process disturbances. Conventional Proportional–Integral–Derivative (PID) control often exhibits limited robustness under such conditions, while advanced strategies such as Nonlinear Model Predictive Control (NMPC) may suffer from sensitivity to model mismatch and disturbances. In this study, an Adaptive Integral Sliding Mode Control (AISMC) strategy is proposed for temperature control of nonlinear gas-phase FBRs. The controller integrates adaptive gain adjustment with an integral sliding surface to improve disturbance rejection and steady-state accuracy while mitigating chattering. The performance of the proposed approach is evaluated through closed-loop simulations over an 18 h dynamic operating scenario involving multiple setpoint changes, catalyst activity variations, and feed flow disturbances. Simulation results demonstrate that AISMC achieves the best overall tracking performance, with a mean absolute error (MAE) of 0.092 K and the lowest maximum temperature deviation among the evaluated controllers. Compared to PID (MAE = 0.794 K) and conventional sliding mode control (MAE = 0.179 K), AISMC provides substantial improvements in transient and steady-state behaviors. In contrast, NMPC exhibits degraded tracking performance (MAE = 0.809 K) under the considered disturbance conditions. All controllers demonstrate sub-millisecond execution times; however, AISMC attains superior accuracy without excessive computational cost. These results indicate that AISMC offers an effective balance between robustness, accuracy, and real-time feasibility for industrial gas-phase polymerization reactors. Full article

In this study, we report a reproducible in situ photochemical method for the simultaneous synthesis of metallic and hybrid metal/metal oxide nanoparticles (NPs) within a UV–curable polymer matrix. A series of epoxy diacrylate-based formulations (BEA) was prepared, consisting of Epoxy diacrylate, Di(Ethylene glycol)ethyl ether acrylate (DEGEEA), and Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO), which served as a Type I photoinitiator. These formulations were designed to enable the simultaneous photopolymerization and photoreduction of metal precursors at various Ag⁺/Co²⁺ ratios, resulting in nanocomposites containing in situ-formed Ag NPs, cobalt oxide NPs, and hybrid Ag–Co₃O₄ nanostructures. The photochemical, magnetic, and dielectric properties of the resulting nanocomposites were evaluated in comparison with those of the pure polymer using UV–Vis and Fourier Transform Infrared Spectroscopy (FT-IR), Photo-Differential Scanning Calorimetry (Photo-DSC), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Impedance Analysis, and Vibrating Sample Magnetometry (VSM). Photo-DSC studies revealed that the highest conversion values were obtained for the BEA-Ag₁Co₁, BEA-Co, and BEA-Ag₁Co₂ samples, demonstrating that the presence of Co₃O₄ NPs enhances polymerization efficiency because of cobalt species participating in redox-assisted radical generation under UV irradiation, increasing the number of initiating radicals and leading to faster curing and higher final conversion. On the other hand, the Ag NPs, due to the SPR band formation at around 400 nm, compete with photoinitiator absorbance and result in a gradual decrease in conversion values. Crystal structures of the NPs were confirmed by XRD analyses. The dielectric and magnetic characteristics of the nanocomposites suggest potential applicability in energy-storage systems, electromagnetic interference mitigation, radar-absorbing materials, and related multifunctional electronic applications. Full article

A sustainable circular pathway was developed for poly(ethylene terephthalate) (PET) nanocomposites through a catalyst-driven polymerization and depolymerization process. In this study, calcium dodecylbenzene sulfonate with n-butyl alcohol modified ZnAl layered double hydroxides (LDHs) were utilized as bifunctional catalysts to synthesize highly exfoliated PET/LDH nanocomposites via in situ polycondensation of bis(2-hydroxyethyl) terephthalate (BHET). The organic modification of LDHs expanded interlayer spacing, improved interfacial compatibility, and promoted uniform dispersion, leading to enhanced mechanical, thermal, and barrier properties. In the second stage, the pristine LDH catalyst efficiently depolymerized the prepared PET/LDH nanocomposites back into BHET through glycolysis, completing a closed-loop BHET-to-BHET cycle. This integrated strategy demonstrates the reversible catalytic functionality of LDHs in both polymerization and depolymerization, reducing metal contamination and energy demand. The proposed approach represents a sustainable route for designing recyclable high-performance PET nanocomposites aligned with the principles of green chemistry and circular material systems. Full article

Accurate knowledge of phase behavior in polyolefin–solvent mixtures is critical for ensuring stable operation and safe scale-up of industrial solution polymerization processes. The binary (n-hexane + ethylene/1-octene copolymer, POE96k-10) and ternary (α-olefin + n-hexane + POE96k-10) phase behaviors were investigated via a visual high-pressure cell (POE96k-10: M_w = 96 kg·mol^–1, M_w/M_n = 3.87, 1-octene mole fraction = 10.31 mol%) at temperatures of 380~480 K and pressures as high as 14 MPa. To systematically analyze the effects of α-olefin mass fraction and type on phase transition, four industrially relevant α-olefins (ethylene, 1-butene, 1-hexene, and 1-octene) were investigated. The results show that the phase transition temperature and pressure for liquid–liquid and liquid–vapor transitions show an approximately linear dependence on α-olefin mass fraction. Ethylene, 1-butene, and 1-hexene lower the phase transition temperature, whereas 1-octene increases it. Ethylene exhibits a strong anti-solvent effect, significantly lowering the transition temperature while increasing the phase transition pressure. The modified Sanchez-Lacombe equation of state (MSL EOS) effectively correlates and reproduces the phase equilibrium data of the α-olefin + n-hexane + POE96k-10 ternary systems, though its accuracy decreases with increasing α-olefin chain length. Full article

This work reports on the synthesis and ring-opening metathesis polymerization (ROMP) of two novel homologous sulfonyl-containing norbornene dicarboximide monomers, specifically, N-4-(trifluoromethylsulfonyl)phenyl-norbornene-5,6-dicarboximide (1a) and N-4-(trifluoromethylsulfonyl)phenyl-7-oxanorbornene-5,6-dicarboximide (1b) using the Grubbs 2nd generation catalyst (I). The polymers are thoroughly characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermomechanical analysis (TMA), thermogravimetric analysis (TGA), atomic force microscopy (AFM), and X-ray diffraction (XRD), among other techniques. A comparative study of gas transport in membranes based on these ROMP-prepared polymers is performed and the gases studied are hydrogen, oxygen, nitrogen, carbon dioxide, methane, ethylene and propylene. It is found that the presence of sulfonyl pendant groups in the polymer backbone increases the gas permselectivity in slight detriment of the gas permeability compared to a polynorbornene dicarboximide lacking sulfonyl groups. The membrane of the sulfonyl-containing polymer with an oxygen heteroatom in the cyclopentane ring, 2b, is also found to have one of the largest permselectivity coefficients reported to date for the separation of H₂/C₃H₆ in glassy polynorbornene dicarboximides. Full article

Hydrophilic interaction liquid chromatography (HILIC) is widely used for the analysis of glycans and oligosaccharides, yet the molecular basis of retention remains incompletely understood. In this study, we investigated dextran ladders labelled with 2-aminobenzamide (2-AB) and Rapifluor-MS™ (Waters, Milford, MA, USA) across a wide range of degrees of polymerization (DP 2–15), temperature conditions (10 °C to 70 °C), and gradient programs using a Acquity™ Premier Glycan BEH Amide column (Bridged Ethylene Hybrid, Waters, Milford, MA, USA). Van’t Hoff analysis revealed distinct enthalpic and entropic contributions to retention, allowing identification of a mechanistic transition from enthalpy-dominated docking interactions at low DP to entropy-driven dynamic adsorption at higher DP. This transition occurred reproducibly between DP 4–6, depending on the fluorescent label, while gradient steepness primarily influenced the location of the minimum enthalpy. Molecular dynamics simulations provided additional evidence, showing increased conformational flexibility and end-to-end distance variability for longer oligomers. This finding is consistent with entropy-dominated adsorption accompanied by displacement of structured interfacial water. Together, these results establish a molecular-level framework linking retention thermodynamics, conformational behavior, and solvation effects, thereby advancing our mechanistic understanding of glycan separation in HILIC. Full article

Poly(ethylene terephthalate) (PET) is a widely used polymer that accumulates in the environment due to its low degradability, requiring efficient recycling strategies. In this study, CaO filler derived from calcium carbide slag (CS) waste was used for the first time as a catalyst for PET depolymerization. PET/CaO composites were prepared via hot extrusion of PET with the finely dispersed CaO filler. The resulting composite demonstrated consistently higher PET conversion (≥95%) and the yields of dimethyl and dibutyl terephthalates (80 and 84%, respectively). Kinetic studies of glycolysis demonstrated that embedding 1 wt% of CaO in the PET matrix doubled the bis(2-hydroxyethyl) terephthalate (BHET) formation rate relative to an externally added CaO catalyst, which resulted in BHET yields of 84.7% and 41.1% after 40 min. SEM and EDX investigations demonstrated good adhesion between the polymer matrix and the filler. The recovered BHET was successfully re-polymerized to produce recycled PET (r-PET). The maximum rate of weight loss of r-PET samples (at T_max = 438.7–444.7 °C) was comparable to the original materials (at T_max = 455.3–457.7 °C). In fact, the direct incorporation of CaO catalyst derived from waste into the polymer matrix during additive manufacturing enabled the implementation of an efficient and scalable closed-loop recycling strategy. Full article

L-Carnitine (L-CAR) and acetyl-L-carnitine (Acetyl L-CAR) are the essential cofactor compounds in lipid metabolism and are used in the treatment of various diseases. The European Food Safety Authority (EFSA) has reported that Acetyl-L-CAR contributes to normal cognitive function and has a beneficial physiological effect. Therefore, the sensitive separation and determination of L-CAR and Acetyl-L-CAR in foodstuffs can provide critical information. A notable trend in modern food analysis is the increasing use of miniaturized analytical columns with a narrow inner diameter (ID). In this study, a new, green analytical method for food analysis was developed to analyze L-CAR and Acetyl-L-CAR in food samples by nano-LC/UV with a hydrophilic monolithic 100 µm ID capillary. This is the first time that the preparation and application of a hydrophilic monolithic nano-column for the analysis of L-CAR and Acetyl-L-CAR in food samples by nano LC/UV has been reported. The hydrophilic monolith was prepared using in situ co-polymerization of glyceryl methacrylate (GMM) and ethylene dimethacrylate (EDMA). Following preparation and characterization, the hydrophilic monolith was used to analyze L-CAR and Acetyl-L-CAR in food samples, including three infant powdered milk samples and five supplements using nano LC/UV. The developed method was validated in terms of precision, sensitivity, linearity, recovery, and repeatability. The LOD and LOQ values were found to be in the range of 0.04–0.09 µg/kg, respectively. In short, the proposed method proved to be suitable for the routine analysis of L-CAR and Acetyl-L-CAR in food samples. Full article