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Hydrogels with or without chemical cross-linking have been studied and used for biomedical applications, such as tissue repair, surgical sealants, and three dimensional biofabrication. These materials often undergo a physical sol–gel or gel–sol transition between room and body temperatures and can also be chemically cross-linked at these temperatures to give dimensional stability. However, few studies have clearly shown the effect of heating/cooling rates on such transitions. Moreover, only a little is known about the effect of cross-linking temperature or the state on the modulus after cross-linking. We have established rheological methods to study these effects, an approach to determine transition temperatures, and a method to prevent sample drying during measurements. All the rheological measurements were performed minimizing the normal stress build-up to compensate for the shrinking and expansion due to temperature and phase changes. We chemically modified gelatin to give gelatin methacryloyl and determined the degree of methacryloylation by proton nuclear magnetic resonance. Using the gelatin methacryloyl as an example, we have found that the gel state or lower temperature can give more rigid gelatin-based polymers by cross-linking under visible light than the sol state or higher temperature. These methods and results can guide researchers to perform appropriate studies on material design and map applications, such as the optimal operating temperature of hydrogels for biomedical applications. We have also found that gelation temperatures strongly depend on the cooling rate, while solation temperatures are independent of the heating rate. [ABSTRACT FROM AUTHOR]

The strain hardening behavior of polymers has important roles in processing such as foaming, film formation, and fiber spinning. The most common method to enhance strain hardening is to introduce a long-chain branching structure on the backbone of a linear polymer, but this method is costly and challenging to tailor the behavior. We hypothesized that in situ shrinking fibers can increase the strain hardening of linear polymers, and the degree can be efficiently controlled. In this study, we show that heat-activated shrinking fibers compounded in linear polypropylene enhance strain hardening and foamability. Moreover, changing processing conditions, such as temperature, can amplify the degree of enhancement. Rheological measurements and physical foaming tests are shown to support our hypothesis. [ABSTRACT FROM AUTHOR]

Plastic pollution has become a global concern, demanding urgent attention and concerted efforts to mitigate its environmental impacts. Biodegradable plastics have emerged as a potential solution, offering the prospect of reduced harm through degradation over time. However, the lower mechanical strength and slower degradation process of biodegradable plastics have hindered their widespread adoption. In this study, we investigate the incorporation of New Zealand (NZ) jade (pounamu) particles into poly(lactic acid) (PLA) to enhance the performance of the resulting composite. We aim to improve mechanical strength, flame retardation, and degradability. The material properties and compatibility with 3D printing technology were examined through a series of characterization techniques, including X-ray diffraction, dispersive X-ray fluorescence spectrometry, scanning electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, 3D printing, compression molding, pycnometry, rheometry, tensile tests, three-point bending, and flammability testing. Our findings demonstrate that the addition of NZ jade particles significantly affects the density, thermal stability, and mechanical properties of the composites. Compounding NZ jade shows two different changes in thermal stability. It reduces flammability suggesting potential flame-retardant properties, and it accelerates the thermal degradation process as observed from the thermogravimetric analysis and the inferred decrease in molecular weight through rheometry. Thus, the presence of jade particles can also have the potential to enhance biodegradation, although further research is needed to assess its impact. The mechanical properties differ between compression-molded and 3D-printed samples, with compression-molded composites exhibiting higher strength and stiffness. Increasing jade content in composites further enhances their mechanical performance. Th results of this study contribute to the development of sustainable solutions for plastic pollution, paving the way for innovative applications and a cleaner environment. [ABSTRACT FROM AUTHOR]

Two tube-based molecular models, the hierarchical 3.0 model and the branch-on-branch model were evaluated for their abilities to predict the behavior of a series of polydisperse, H-shaped, 1,4-polybutadienes. The samples had been synthesized using a novel technique designed to suppress the generation of high molar mass by-products. While size exclusion chromatography data indicated that the samples were monodisperse, low molar mass by-products were later revealed by temperature gradient interaction chromatography. Viscoelastic data were obtained at temperatures ranging from -75 °C to 25 °C, and the samples were found to be thermorheologically simple. Sensitivity and uncertainty analyses revealed that among the model parameters, the value of plateau modulus has the strongest effect on model predictions. As molecular models improve, it will become ever more essential to evaluate them using accurate data on materials whose microstructures have been reliably established. This is especially important for materials that are structurally polydisperse. [ABSTRACT FROM AUTHOR]

We studied polymer-polymer interfacial slip in bilayer films of highly immiscible (interaction parameter, χ≅0.1) polyethylene and fluoropolymer from medium to higher shear stresses (10-200 kPa) using both visualization and stress reduction. We found good agreement between results from the two methods as well as with previous studies using multilayers by Lee et al. [J. Rheol. 53, 893-915 (2009)] and visualization of flow in a transparent capillary by Migler et al. [J. Rheol. 45, 565-581 (2001)]. We observed two power-law regions: Vslip∝τ6.2 with a transition to Vslip∝τ1.8 at 50 kPa. This is in contrast to the theory of Brochard-Wyart and de Gennes [C. R. Acad. Sci., Ser. II: Mec., Phys., Chim., Sci. Terre Univers 317, 13-17 (1993)], which predicts a transition from infinite slope to a slope of one at a critical stress. [ABSTRACT FROM AUTHOR]

Strain hardening has important roles in understanding material structures and polymer processing methods, such as foaming, film forming, and fiber extruding. A common method to improve strain hardening behavior is to chemically branch polymer structures, which is costly, thus preventing users from controlling the degree of behavior. A smart microfiber blending technology, however, would allow cost-efficient tuning of the degree of strain hardening. In this study, we investigated the effects of compounding polymers with microfibers for both shear and extensional rheological behaviors and characteristics and thus for the final foam morphologies formed by batch physical foaming with carbon dioxide. Extensional rheometry showed that compounding of in situ shrinking microfibers significantly enhanced strain hardening compared to compounding of nonshrinking microfibers. Shear rheometry with linear viscoelastic data showed a greater increase in both the loss and storage modulus in composites with shrinking microfibers than in those with nonshrinking microfibers at low frequencies. The batch physical foaming results demonstrated a greater increase in the cell population density and expansion ratio with in situ shrinking microfibers than with nonshrinking microfibers. The enhancement due to the shrinkage of compounded microfibers decreasing with temperature implies that the strain hardening can be tailored by changing processing conditions. [ABSTRACT FROM AUTHOR]

Biodegradable plastics are thought to be the possible directions in managing plastic pollutions. Unfortunately, they are not recycled in most countries since they are designed to decompose even though recycling is a more pragmatic method than landfill or incineration. Thus, it is more constructive to develop methods to recycle biodegradable plastics or to develop biodegradable yet recyclable plastics. In this study, we used cutlery with a composite of poly(lactic acid) (PLA) and talc. The possibility to recycle it to make foams was studied even though it will have lowered mechanical strength from the recycling process as it is less significant for this product. Tensile properties of solid PLA and foams showed no significant decrease in the strength up to three processes of compression molding and foaming. We performed shear rheometry to determine the thermal stability and dependences of the complex viscosity on frequency and temperature. The magnitude of the complex viscosity dramatically increased with decreasing frequency and such an upturn increased with temperature, but time-temperature superposition was valid at high temperatures. The extensional rheometry showed no strain hardening, but physical foaming using supercritical carbon dioxide (CO2) could still occur, and the operating conditions to obtain various foamed structures were determined. We also compared the effects of one-directional against three-dimensional expansion. Overall, the concentration of CO2 in PLA and crystallinity of the foams are the two key variables to describe the bulkiness of foams. Surprisingly, the lower the CO2 concentration, the bulkier the foams at any sorption temperature and pressure. [ABSTRACT FROM AUTHOR]

Various commercial zeolites, including FER, MOR, ZSM‐5, BEA, and FAU frameworks, were treated with NH4F aqueous solutions to study the effects of fluoride etching on different zeolite frameworks. NH4F‐treated small‐medium pore FER, MOR, and ZSM‐5 samples showed much higher mesoporosities than the untreated ones without alteration of the structural compositions and acidic properties. On the other hand, the 12‐membered ring zeolites BEA and FAU showed severe dissolution of the framework aluminosilicate structure after NH4F etching due to the high accessibility of fluoride species into the framework structures. The effect of NH4F concentration on the fluoride treatment of H‐ZSM‐5 zeolite was specifically studied. From the results, we observed that structural etching with 20 wt % NH4F was optimal for fabricating open‐pore H‐ZSM‐5 zeolite and resulted in a high mesoporosity with comparable relative crystallinity and acidity with respect to the untreated H‐ZSM‐5. The catalytic activities of the open‐pore H‐ZSM‐5 were evaluated with acid‐catalyzed methanol and bioethanol conversions. Remarkably, the hierarchical open‐pore H‐ZSM‐5 zeolite fabricated via fluoride etching exhibited an enhanced catalytic performance in bioethanol conversion with >85 % conversion over 34 h TOS and a higher catalytic stability in methanol conversion than the parent H‐ZSM‐5 (~50 % of bioethanol conversion at 34 h TOS). [ABSTRACT FROM AUTHOR]

Publisher's Note: "Recycling and rheology of poly(lactic acid) (PLA) to make foams using supercritical fluid" [Phys. Comparison of the top view of the cell structure after cutting samples in the direction that is parallel to the bottom surface [Fig. This article was originally published online on 29 June 2021 with an error in the captions for Figs. [Extracted from the article]

This article, published in ChemCatChem, explores the modification of zeolite morphology through NH4F etching for catalytic bioalcohol conversion. The researchers investigated the effects of fluoride etching on small and medium pore zeolites like FER, MOR, and ZSM-5, finding that it created mesoporosity while retaining structural integrity and acidic properties. However, they also observed adverse effects on large pore zeolites like FAU, leading to the breakdown of the microporous framework. The study highlights the complex relationship between zeolite framework, etching process, and catalytic efficiency. [Extracted from the article]

Gases or supercritical fluids (SCF) are widely used in polymer science and engineering, as their dissolution into polymeric materials will alter their inherent thermal properties; including melting and crystallization temperatures (T m and T c). One possible method to determine these temperatures, at elevated pressures, is to use a high-pressure differential scanning calorimeter (HP-DSC). However, the elevated pressures used in HP-DSC may result in signal instabilities, limiting the testing window for these pressures. This study presents a novel testing system using dielectric measurements to determine the effects of dissolved gas/SCF on the T m and T c of polymers. We have developed an instrument to determine the dielectric properties of both polymer/gas and polymer/SCF mixtures, at elevated pressures and temperatures. Using the change in the measured dielectric constant or loss, T m and T c were determined. The effects of hydrostatic pressure and plasticization due to dissolved carbon dioxide (CO 2) and Helium (He) on the T m and T c of high density polyethylene (HDPE) are presented and discussed. Both T m and T c increase with pressure and decrease due to plasticization, i.e., pressure and plasticization are competing variables. The dissolution of He, having a low solubility into HDPE, reveals that pressure is the dominant effect. In contrast, the dissolution of CO 2 , having a high solubility into HDPE, shows that plasticization is predominant. • Developed a novel system for polymer dielectric property measurements at high temperatures and high pressures. • Build the relationship between thermal property and dielectric property of the HDPE and gas/supercritical fluids mixture. • Analyzed CO 2 's plasticization and hydrostatic pressure effects on high density polyethylene. [ABSTRACT FROM AUTHOR]

Allogeneic lung transplant is limited both by the shortage of available donor lungs and by the lack of suitable long-term lung assist devices to bridge patients to lung transplantation. Avian lungs have different structure and mechanics resulting in more efficient gas exchange than mammalian lungs. Decellularized avian lungs, recellularized with human lung cells, could therefore provide a powerful novel gas exchange unit for potential use in pulmonary therapeutics. To initially assess this in both small and large avian lung models, chicken (Gallus gallus domesticus) and emu (Dromaius novaehollandiae) lungs were decellularized using modifications of a detergent-based protocol, previously utilized with mammalian lungs. Light and electron microscopy, vascular and airway resistance, quantitation and gel analyses of residual DNA, and immunohistochemical and mass spectrometric analyses of remaining extracellular matrix (ECM) proteins demonstrated maintenance of lung structure, minimal residual DNA, and retention of major ECM proteins in the decellularized scaffolds. Seeding with human bronchial epithelial cells, human pulmonary vascular endothelial cells, human mesenchymal stromal cells, and human lung fibroblasts demonstrated initial cell attachment on decellularized avian lungs and growth over a 7-day period. These initial studies demonstrate that decellularized avian lungs may be a feasible approach for generating functional lung tissue for clinical therapeutics. [ABSTRACT FROM AUTHOR]