Increase In Crosslink Density Research Articles

Tribomechanical Properties of PVA/Nomex® Composite Hydrogels for Articular Cartilage Repair

Due to the increasing prevalence of articular cartilage diseases and limitations faced by current therapeutic methodologies, there is an unmet need for new materials to replace damaged cartilage. In this work, poly(vinyl alcohol) (PVA) hydrogels were reinforced with different amounts of Nomex® (known for its high mechanical toughness, flexibility, and resilience) and sterilized by gamma irradiation. Samples were studied concerning morphology, chemical structure, thermal behavior, water content, wettability, mechanical properties, and rheological and tribological behavior. Overall, it was found that the incorporation of aramid nanostructures improved the hydrogel’s mechanical performance, likely due to the reinforcement’s intrinsic strength and hydrogen bonding to PVA chains. Additionally, the sterilization of the materials also led to superior mechanical properties, possibly related to the increased crosslinking density through the hydrogen bonding caused by the irradiation. The water content, wettability, and tribological performance of PVA hydrogels were not compromised by either the reinforcement or the sterilization process. The best-performing composite, containing 1.5% wt. of Nomex®, did not induce cytotoxicity in human chondrocytes. Plugs of this hydrogel were inserted in porcine femoral heads and tested in an anatomical hip simulator. No significant changes were observed in the hydrogel or cartilage, demonstrating the material’s potential to be used in cartilage replacement.

Preparation and characterization of UV-curable coatings based on waterborne polyurethane acrylate/g-C3N4 co-crosslinked network for wood materials

Wood materials are often damaged due to exposure to environmental factors including humidity changes, temperature fluctuations, and ultraviolet radiation, resulting in surface aging, deformation, and cracking. Therefore, developing a new wood coating with good mechanical properties and weather resistance is conducive to improving the usability and service life of wood as an outdoor material. In this study, graphitic carbon nitride (g-C3N4) with a characteristic crystal structure was synthesized using melamine as raw material. By constructing a g-C3N4 /polyurethane acrylate co-crosslinked network, a UV-curable wood coating with excellent interfacial adhesion was prepared, which retained the natural aesthetic texture of the wood and imparted good wear resistance, anti-wetting property, and aging resistance to the wood material. Subsequently, the formation process and cross-linking reaction mechanism of the coating were revealed by XRD, FTIR and XPS measurements. Compared with untreated samples, coatings with a cross-linked network structure exhibited enhanced resistance to external environmental changes. As the content of the g-C3N4 increased (>1.0 %), the mechanical properties were significantly improved, with the mass loss rate and damaged area decreasing by 56.9 % and 60.0 %. Meanwhile, with the increased cross-link density of the coating, the water and heat resistance of the wood increased by 22.77 % and 260 %, respectively. After a seven-day UV aging resistance test, the ΔE values only changed by 10.28 %, showing good weathering resistance. This design and synthesis of wood coating provides an effective technology for the long-term use of outdoor wood material.

Effects of NIR-reflective pigments on waterborne polyurethane coatings and their thermal insulation performance

Waterborne coatings have garnered much attention and gradually occupied the coating market recently due to the significant advantages in volatile organic compound emissions compared with solvent-borne coatings. Waterborne polyurethane coatings are a majority portion of waterborne coatings. Unlike solvent-borne coatings, the film formation of waterborne coatings occurs in an inhomogeneous phase, which brings a challenge for pigmentation in waterborne coatings. However, the influence of pigment on film formation and the property of waterborne polyurethane coating remain unclear. In this study, the different contents of commercial black near-infrared (NIR) reflective pigments were incorporated into both commercial and synthetic waterborne polyurethane systems. The film formation process was monitored by multispeckle diffusing wave spectroscopy. The impact of the pigment content on dry films was assessed through scanning electron microscope, color and gloss measurements, dynamical thermal analyzer, and tensile testing. Furthermore, the thermal insulation performance of the waterborne polyurethane coatings was evaluated to study the function of the NIR reflective pigments. Our findings reveal that the addition of black NIR reflective pigments yields a multifaceted effect on film formation and coating morphology and improves thermal insulating property. Elevated pigment content correlated with increased crosslinking density, tensile stress, and Young's modulus.

Increasing the cross-link density in a dual dissociative and associative polythiourethane covalent adaptable network improves both creep resistance and extrudability

There have been significant, recent reports of the effects of cross-link density on the relaxation dynamics and processability of exclusively associative covalent adaptable networks (CANs), also called vitrimers. Similar characterization is lacking for the substantial number of CANs that exhibit dual associative and dissociative dynamic covalent chemistries. Polythiourethane (PTU), which is a thiol-based analogue of polyurethane, is one such polymer class that exhibits both dissociative and associative dynamic chemistries. Here, we tune the cross-link density of PTU CANs by systematic incorporation of long-chain and short-chain thiols. As would be commonly expected, relative to networks with lower cross-link density, PTU networks with higher cross-link density exhibit improved creep resistance at 60 °C and 100 °C. However, we also observe faster elevated-temperature stress relaxation with increasing cross-link density, which is attributable to the dual nature of the PTU dynamic chemistry, with the associative dynamic mechanism being increasingly favored and becoming increasingly more rapid with increasing cross-link density. Because of this shift, our PTU CAN with the highest cross-link density undergoes facile melt extrusion at 150 °C; in contrast, our PTU CAN of lowest cross-link density cannot be melt extruded. Overall, this work highlights the significance of cross-link density in networks exhibiting two or more dynamic chemistries and how that may lead to otherwise unexpected outcomes, e.g., better processability at higher cross-link density.

Emerging Mo-doped MgAl-LDH lamellar/carbon nanotubes as 3D sustainable nanohybrid for designing a durable smart anti-corrosion composite

This paper focused on the utilization of 3D hybrid nanocomposites composed of layered double hydroxides (L) containing sodium molybdate (SM), which are chemically bonded with functionalized multi-walled carbon nanotubes (FCN), as nanocarriers for smart corrosion prevention. The SM molecules were loaded into the L, and L/FCN nanocarriers by an anion exchange process, and then the 3 synthesized nanoparticles (i.e., L, SM-L, and SM-L/FCN) were characterized. Following the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PD) tests' outcomes, the maximum corrosion prevention efficiency (about 90.88 %) belongs to the SM-L/FCN nano reservoir containing saline extract. Additionally, for the epoxy phase, the EIS results (on the intact and scratched specimens) revealed a significant diminish in the chloride and water penetration into the epoxy coating during 63 days of immersion. EIS results indicated the enhancement of the charge transfer resistance (Rct) of the scratched coatings, from 17.42 kΩ.cm2 for the EP sample to 72.47 kΩ.cm2 for the SM-L/FCN/EP one in long immersion times, revealing the self-repairing behavior of the designed coating. The results of intact coating revealed that the Log (|Z|0.01 Hz) value reached 10.63 in long immersion time indicating a decreased occurrence of coating disbondment attributed to the electrolyte infiltration and corrosion of the underlying metal substratum. According to the pull-off and cathodic disbonding tests results, there was an enhancement in adhesion (51.5 % decrease in loss of adhesion strength, & a 52 % decline in diameter of cathodic disbondment), and a strong interaction between the interface of epoxy and substratum. According to the mechanical tests (Tensile and DMTA) results the incorporation of L and FCN nanoparticles into the SM-L/FCN sample enhanced the nanocomposite's mechanical properties. The tensile test showed an increase in ultimate tensile strength (σUTS) and elongation at break (Ɛb) of 130.61 % and 107.59 %, respectively, compared to the pure epoxy (EP) sample. Additionally, the dynamic mechanical thermal analysis (DMTA) test indicated a 144 % increase in crosslinking density for the SM L/FCN sample compared to the neat epoxy.

Development of single-component epoxy resin with superb thermal stability, flame retardancy, smoke suppression, and latency via Cu-based phosphorus/imidazole-containing complex

To address the growing need for fire-safe single-component epoxy resin (EP) systems, this study introduced a phosphorus-containing copper complex (Cu-DA) as a multifunctional latent curing agent. The Cu-DA complex, synthesized by coordinating copper (II) chloride and a phosphorus-based imidazole, significantly improved the latency, thermal stability, and fire resistance of single-component EP. The obtained EP/Cu-DA-2 mixture with 15.3 wt% Cu-DA showed a 43-day shelf life and a rapid gel time of 22 minutes at 150°C, highlighting its superb latency and fast curing. After curing, the resultant thermoset had a high glass transition temperature of 160.9°C and increased crosslinking density, indicating superior thermal stability. The EP/Cu-DA-3 system with 17.4 wt% Cu-DA achieved a high limiting oxygen index (LOI) of 37.8% and a UL-94 V-0 rating, reflecting its satisfactory flame retardancy. Furthermore, compared to the control EP system, the total smoke production (TSP) and maximum smoke density (MSD) of EP/Cu-DA-3 were reduced by approximately 28.4% and 25.8%, respectively, demonstrating significantly enhanced smoke suppression. The research offers a scalable strategy for developing single-component EP systems with rapid curing, high fire resistance, and great smoke suppression, meeting the demands of industrial applications.

Effect of Peptide-Polymer Host-Guest Electrostatic Interactions on Self-Assembling Peptide Hydrogels Structural and Mechanical Properties and Polymer Diffusivity.

Peptide-based supramolecular hydrogels are an attractive class of soft materials for biomedical applications when biocompatibility is a key requirement as they exploit the physical self-assembly of short self-assembling peptides avoiding the need for chemical cross-linking. Based on the knowledge developed through our previous work, we designed two novel peptides, E(FKFE)2 and K(FEFK)2, that form transparent hydrogels at pH 7. We characterized the phase behavior of these peptides and showed the clear link that exists between the charge carried by the peptides and the physical state of the samples. We subsequently demonstrate the cytocompatibility of the hydrogel and its suitability for 3D cell culture using 3T3 fibroblasts and human mesenchymal stem cells. We then loaded the hydrogels with two polymers, poly-l-lysine and dextran. When polymer and peptide fibers carry opposite charges, the size of the elemental fibril formed decreases, while the overall level of fiber aggregation and fiber bundle formation increases. This overall network topology change, and increase in cross-link stability and density, leads to an overall increase in the hydrogel mechanical properties and stability, i.e., resistance to swelling when placed in excess media. Finally, we investigate the diffusion of the polymers out of the hydrogels and show how electrostatic interactions can be used to control the release of large molecules. The work clearly shows how polymers can be used to tailor the properties of peptide hydrogels through guided intermolecular interactions and demonstrates the potential of these new soft hydrogels for use in the biomedical field in particular for delivery or large molecular payloads and cells as well as scaffolds for 3D cell culture.

Castor oil-based polyurethane Vitrimer modified asphalts regulated by dual dynamic reversible reactions and crosslinking density: Preparation, basic assessment and self-healing behavior

Thermosetting polymers, commonly used to improve asphalt properties, bring excellent pavement performance, but also pose significant challenges to the healing and recyclability of their modified asphalts after long-term service. An effective approach involves introducing dynamic bonds into the crosslinking networks to synthesize Vitrimer-modified asphalts with self-healing response. Due to the splendid mechanical properties, high elasticity, flexibility and easily controllable cross-linked structure of polyurethane, a novel castor oil-based polyurethane Vitrimer modified asphalt with disulfide bonds and Diels-Alder reactions was developed. Based on the prepared castor oil-based polyurethane Vitrimer (C-PUV, composed of components A and B) and its modified asphalts (C-PUVAs), a comprehensive study was conducted on the crosslinking density, mechanical properties, thermal stability, viscosity, compatibility, rheological properties, and self-healing behavior. The results indicated that C-PUVAs (C-PUVA1/C-PUVA2/C-PUVA3/C-PUVA4) exhibited sufficient retention times for viscosity, uniform phase distribution, and good high-temperature performance. The damaged C-PUVAs achieved a mechanical strength recovery rate more than 75 % after the first cycle of self-healing at 80 ℃ and 0.3 MPa. Furthermore, the crosslinking density of C-PUV was regulated by the segment length of component B. As the crosslinking density increased, C-PUV and C-PUVAs obtained higher mechanical strength while sacrificing part of self-healing efficiency. The mechanism is that increased crosslinking density altered the gel point distributions of the reversible crosslinked networks, resulting in a longer relaxation time and higher activation energy. In conclusion, the above findings provided valuable insights for developing bio-based polyurethane Vitrimer modified asphalts, and endosing thermosetting polymer modified asphalts with self-healing and recyclable properties.

Accelerating effect of metal ionic liquids for epoxy-anhydride copolymerization

One of the main drawbacks of high-performance epoxy-anhydride thermosets is slow cross-link kinetics requiring high temperature and long curing cycle. Herein, the accelerating effect of imidazolium metal-based ionic liquids (MILs) bearing (FeCl4)-, (ZnCl4)2-, and (CoCl4)2- anions on epoxy-anhydride copolymerization was investigated. It was observed that MILs accelerated bisphenol diglycidyl ether (DGEBA) − methylhexahydrophthalic anhydride (MHHPA) cross-linking, better than the reference catalysts (1-methylimidazole and 1-butyl-3-methylimidazolium chloride), especially at low temperatures through their ability to activate a rapid anhydride ring opening and formation of carboxyl groups, which initiates polyesterification. A detailed investigation of the polymerization mechanism revealed the formation of alternating epoxy-anhydride copolymers although several MILs-induced initiation mechanisms were detected. Despite the multiple-initiation consisting of imidazole, counter anion, and polyesterification pathways, the cross-linking kinetics was successfully fitted up to vitrification by the Kamal-Sourour model. Finally, MILs-induced cross-linking leads to homogeneous network build-up enabling to produce thermosetting materials with an increased cross-link density, a glass transition temperature above 150 °C, and excellent thermal stability.

The Role of Reduced Graphene Oxide in Enhancing the Mechanical and Thermal Properties of a Rubber Cover Joint.

The development of high-performance rubber composites has always been a research hotspot in the field of conveyor belt manufacturing. In this work, a rubber cover joint composite made of reduced graphene oxide (rGO) was prepared using latex mixing and mechanical blending methods, with a steel wire rope conveyor belt as the research object, and the influence of the rGO content on the properties of the rubber composite is discussed. The structure and morphology characterization of the rGO/NR rubber show that the addition of rGO does not change its crystal structure, and 1.2 phr rGO is uniformly dispersed throughout the rubber composite. As more rGO is added, the mechanical properties of the rGO rubber cover joint first improve and then worsen. With the addition of 1.2 phr, the cross-linking density increases by 80.6%, the tensile strength of the rubber composites increases by 49.7%, the elongation at break increases by 23.6%, and the adhesion strength increases by 12.4%. The tensile strength of the rGO rubber cover joint can still maintain 72.5% of its pre-thermal aging value. The wear resistance and thermal conductivity increase as more phr is added. When 3.0 phr is added, the wear resistance of the rubber composites increases by 32.9%, the thermal conductivity increases by 118.8%, and the temperature difference at the completion of vulcanization decreases from 4.5 °C to 1.8 °C. The results show that when 1.2 phr of rGO is added, the rubber conveyor belt joint obtains the best comprehensive performance. These enhanced comprehensive properties allow for the practical application of rGO nanomaterials to conveyor belt rubber.

Biological and Mechanical Performance of Dual-Setting Brushite-Silica Gel Cements.

Bone defects resulting from trauma, diseases, or surgical procedures pose significant challenges in the field of oral and maxillofacial surgery. The development of effective bone substitute materials that promote bone healing and regeneration is crucial for successful clinical outcomes. Calcium phosphate cements (CPCs) have emerged as promising candidates for bone replacement due to their biocompatibility, bioactivity, and ability to integrate with host tissues. However, there is a continuous demand for further improvements in the mechanical properties, biodegradability, and bioactivity of these materials. Dual setting of cements is one way to improve the performance of CPCs. Therefore, silicate matrices can be incorporated in these cements. Silicate-based materials have shown great potential in various biomedical applications, including tissue engineering and drug delivery systems. In the context of bone regeneration, silicate matrices offer unique advantages such as improved mechanical stability, controlled release of bioactive ions, and enhanced cellular responses. Comprehensive assessments of both the material properties and biological responses of our samples were conducted. Cytocompatibility was assessed through in vitro testing using osteoblastic (MG-63) and osteoclastic (RAW 264.7) cell lines. Cell activity on the surfaces was quantified, and scanning electron microscopy (SEM) was employed to capture images of the RAW cells. In our study, incorporation of tetraethyl orthosilicate (TEOS) in dual-curing cements significantly enhanced physical properties, attributed to increased crosslinking density and reduced pore size. Higher alkoxysilyl group concentration improved biocompatibility by facilitating greater crosslinking. Additionally, our findings suggest citrate's potential as an alternative retarder due to its positive interaction with the silicate matrix, offering insights for future dental material research. This paper aims to provide an overview of the importance of silicate matrices as modifiers for calcium phosphate cements, focusing on their impact on the mechanical properties, setting behaviour, and biocompatibility of the resulting composites.

Organic-inorganic hybrid epoxy resin coating with high thermal stability and hydrophobicity for corrosion protection prepared by (3-aminopropyl) triethoxysilane as a bridging agent

The corrosion protection application of epoxy resin (EP) in high-temperature environments is greatly restricted due to thermal stability limit and inherent hydrophilicity. In this study, a hybrid epoxy resin was synthesized by grafting hexadecyltrimethoxysilane (HDTMS), 1 H,1 H,2 H,2 H-perfluorodecyltrimethoxysilane (PFDTMS), and tetraethyl orthosilicate (TEOS) onto the molecule of epoxy resin, using (3-aminopropyl) triethoxysilane (APTES) as a bridging agent. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses revealed the presence of C-N bonds and Si-O-Si bonds in the hybrid epoxy resin, confirming the success of the hybridization. Compared to pure epoxy resin, the hybrid epoxy resin coating effectively enhances the thermal stability while maintaining both corrosion resistance and hydrophobicity. Thermal gravimetric analysis (TGA) indicated that the initial decomposition temperature (T5%) of the hybrid epoxy resin coating increased from 327°C to 372°C. This enhancement is attributed to the introduction of Si-O-Si bonds and an increase in cross-linking density in the hybrid epoxy resin. Water contact angle measurements showed that with the introduction of C-F bonds and long carbon chains, the contact angle increased from 71° to 106°. The hydrophobic hybrid epoxy resin coating maintained a contact angle of 100° at 300°C for 300 hours. The transition from hydrophilicity to hydrophobicity improves the corrosion resistance of the coating.

Advancing flame retardancy, mechanical properties, and hydrophobicity of epoxy resins through bio-based cinnamaldehyde derivative

Developing flame retardants based on biomass materials to improve the flame retardancy and multifunctionality of epoxy resin (EP) is crucial. Herein, we synthesized a novel derivative, PPABCA, combining cinnamaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to serve as flame retardants for EP. Incorporating 5 wt% PPABCA into EP (EP/PPABCA-5) demonstrated remarkable flame retardancy, with a limiting oxygen index of 33.7% and a V-0 rating in UL-94 test. It also reduced the peak heat release rate, total heat release, and peak CO2 production by 32.9%, 29.9%, and 42.8%, respectively. The enhanced flame retardancy was facilitated by the capture of phosphorus-containing free radicals coupled with dilution of combustible gas characterized by the blow-out phenomenon and formation of a dense char layer enriched with triazine and phosphorus. Furthermore, EP/PPABCA-5 exhibited enhanced flexural and tensile strengths by 20.5% and 16.5% compared to EP, attributed to the increased cross-linking density and π-π conjugation from the high rigidity of PPABCA, along with its good compatibility with EP. Additionally, the improved hydrophobic properties of PPABCA, confirmed by electrostatic potential analysis, further enhanced the hydrophobicity of EP composites. Overall, this work underscored a strategic development of multifunctional, bio-based flame retardant, showcasing efficient flame retardancy, enhanced mechanical properties, and boosted hydrophobicity in EP.

Biomass carboxylic acid modified hydrotalcites for improving the mechanical strength and recyclability of 100 % biobased carbon content epoxy soybean oil based vitrimers

To realize the demand of sustainable development in materials industry, vitrimers deriving from epoxidized soybean oil (ESO) have received considerable attention because of their environmentally friendly and renewable. However, they suffer from poor mechanical strength and non-reprocessability, which confine their application. Herein, a facile design of 100 % bio-based carbon contents vitrimers incorporating ESO and citric acid modified layered double hydroxides (CA-LDHs) was proposed, which showing good mechanical properties and accelerated stress relaxation. Optimal performances of vitrimers with best tensile strength, curing and repairing efficiency were obtained at 20 wt% CA-LDHs loading. The tensile strength of 20EC-CLE increased by 233 % compared with pure EC-E due to the reinforcing effect of CA-LDHs and the increased cross-linking density. Benefit from the abundant Al3+ catalytic sites and large contact areas of the CA-LDHs lamella, the vitrimers showed an excellent curing and 82 % reprocessing efficiency. Interestingly, the precursor of the vitrimers was used as an adhesive layer for polyvinyl chloride (PVC) leather and provided 3.4 ± 0.4 N/cm peel strength and bonding reproducibility.

Role of crosslinkers on the properties of bio‐based wood adhesives

AbstractAs people became more conscious of the risks associated with pollution in the early 21st century, eco‐friendly adhesives made from plant oil began to be used. Bio‐based adhesives are widely used due to their low price, easy accessibility, and high biodegradability; however, their low adhesive strength is an issue. This work incorporates three natural crosslinkers: tannic acid (TA), sorbitol (SR), and cellulose (CL) to address the drawbacks of bio‐based adhesives, such as low adhesive strength, inferior output in humidity and longer curing time that result from excess water. Methylene diphenyl diisocyanate (MDI) was used to react with soybean oil‐based polyol (SOP) plus the crosslinkers to make bio‐based polyurethane adhesives. The maximum bonding strength of the soybean‐based adhesive containing 10 wt.% of SR (SR‐10%) was measured at 6.19 MPa which is about 44% higher than the sample without SR. The higher strength is due to the crosslinking ability of SR. The effect of crosslinking is also observed in the study of polar protic and polar aprotic solvents used to dissolve the adhesive. As compared with the polar aprotic solvent tetrahydrofuran, TA‐containing adhesive samples showed a maximum tensile strength of 3.69 MPa in methanol; a polar protic solvent that can participate in further hydrogen bonding to form a higher crosslinked complex. The glass transition temperature (Tg) increases with the increase in crosslinker amount. The observed increase in Tg may be attributable to an increase in crosslinking density, which reduces polymer chain flexibility and causes a stronger material.Highlights Bio‐adhesives based on soybean oil and diisocyanate were synthesized. Natural crosslinking agents such as tannic acid, sorbitol, and cellulose were used. The effect of crosslinking using polar protic and aprotic solvents was studied. The glass transition temperature increases with the increase in crosslinker amount.

Preparation of strong, UV-blocking and sustainable glucose-cross-linked cellulose plastics via hydroxyl-yne click reaction

The construction of functional cellulose plastics possessing strong UV-blocking, hydrophilicity, and biodegradability is challenging. Therefore, we provide a novel strategy to successfully prepare sustainable and hydrophilic glucose-cross-linked cellulose (GC) plastics showing effective UV-blocking and excellent mechanical properties via hydroxyl-yne click reaction at room temperature. The results demonstrated that hydroxyl-yne click chemistry enabled efficient crosslinking of cellulose with glucose using 4-dimethylamino pyridine (DMAP) as a catalyst. Moreover, the DMAP residue imparted good UV-shielding properties to GC films exhibiting nearly 100 % UVC (200–275 nm) and 100 % UVB (320–275 nm) shielding ratios. The introduction of glucose imparted superior hydrophilicity (water contact angle of 40.3–43.2°) and improved water adsorption. Additionally, the mechanical properties of the GC films increased with the increasing crosslinking density, and the highest tensile stress was 94 MPa. The water-induced breaking and hydrogen bond reforming strategy led to a stress of 127 MPa and a strain of 25.6 % for the final GC2 film, which were excellent compared to those of the most reported cellulose films. Additionally, GC films were biosafe, exhibited improved oxygen barrier, and good biodegradability. Hence, this study provides a promising and efficient approach for preparing high-performance cellulose plastics.

Organic radicals stabilization in natural rubber: Discerning the influence of thermo-oxidation using chemically modified or unmodified lignin as antioxidant

We have implemented a lignin compatibilization strategy through silylation and elaborated NR compounds with lignin and silylated lignin. Then, the lignin’s contribution to the preservation of physico-mechanical properties and stability of the materials obtained against thermo-oxidation was studied. Thus, our work considered the indirect study of the antioxidant activity on NR compounds by determining the physico-mechanical properties before and after accelerated thermo-oxidative aging, which allowed us to determine that the increase in crosslinking density during the initial hours of accelerated aging was the main observed cause associated with a higher tensile strength retention rate (TSRR: 13.4 %) in NR compound with 5 phr of lignin (CL5) versus a TSRR: 4.7 % for the compound with 5 phr of silylated lignin (CL5Si1). On the other hand, the direct study of the antioxidant capacity by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) using oxygen atmosphere indicated greater thermal stability in NR compounds when lignin is not silylated. The maximum degradation temperature for the CL5 compound was 341.6 °C, while for the CL5Si1 compound it was 328.6 °C. The oxidation induction temperature (OITtemp) in the CL5 compound was 190.9 °C with a peak at 221.0 °C, while for CL5Si1 it was 170.3 °C with a peak at 194.1 °C, indicating again that unsilylated lignin is more suitable as an antioxidant. Finally, through Electron Paramagnetic Resonance (EPR), we determined that the radical quenching effect due to the presence of lignin was significant as the lignin content increases, with a reduction in radical presence close to 50 % compared to a reference compound without lignin.

Novel multifunctional highly crosslinked bio-based waterborne polyurethane networks modified via long fatty hydrophobic side chains

The mechanical properties and water resistance of castor oil-based waterborne polyurethane are mutually limited due to the presence of a hydrophilic chain extender. Herein, Arbutin (AT) was used as a crosslinking agent, and benzimidazole (CR-455) was utilized as an ultraviolet absorber, sustainable long fatty hydrophobic chain extenders, sorbitan monooleate (SP), glycerol laurate (GML), glycerin monostearate (GMS), and trimethylolpropane monooleate (TPM), were introduced into castor oil-based waterborne polyurethane (CWPU) backbones through molecular structure design respectively. Subsequently, the amount of SP was changed to prepare a series of waterborne polyurethane dispersions, and their emulsion and film properties were thoroughly investigated. The finding showed that the incorporation of long fatty hydrophobic chain extenders led to an increase in crosslinking density, thereby endowing CWPU films with good mechanical properties, water resistance, and anti-corrosion efficacy. Moreover, the bio-based content in the CWPU film had reached an impressive 90.9 %. The addition of SP content resulted in a gradual improvement in the mechanical properties, water resistance, and corrosion resistance of CWPU-SP films. When the SP content was 40 %, due to the high strength of hydrogen bonds and the density of crosslinking in systems, the tensile strength, toughness, water absorption rate, and corrosion protection efficiency of the CWPU-SP40 film reached 18.1 MPa, 20 MJ/m3,7.7 %, and 98.47 %, respectively. Particularly, the prepared transparent CWPU films exhibited complete UV shielding. This work would pave the way for the application of bio-based waterborne polyurethanes in high-performance coatings, such as anti-corrosion and sunscreen.

The Facile Synthesis and Application of Mesoporous Silica Nanoparticles with a Vinyl Functional Group for Plastic Recycling.

Due to growing concerns about environmental pollution from plastic waste, plastic recycling research is gaining momentum. Traditional methods, such as incorporating inorganic particles, increasing cross-linking density with peroxides, and blending with silicone monomers, often improve mechanical properties but reduce flexibility for specific performance requirements. This study focuses on synthesizing silica nanoparticles with vinyl functional groups and evaluating their mechanical performance when used in recycled plastics. Silica precursors, namely sodium silicate and vinyltrimethoxysilane (VTMS), combined with a surfactant, were employed to create pores, increasing silica's surface area. The early-stage introduction of vinyl functional groups prevented the typical post-synthesis reduction in surface area. Porous silica was produced in varying quantities of VTMS, and the synthesized porous silica nanomaterials were incorporated into recycled polyethylene to induce cross-linking. Despite a decrease in surface area with increasing VTMS content, a significant surface area of 883 m2/g was achieved. In conclusion, porous silica with the right amount of vinyl content exhibited improved mechanical performance, including increased tensile strength, compared to conventional porous silica. This study shows that synthesized porous silica with integrated vinyl functional groups effectively enhances the performance of recycled plastics.

Mechanically resilient hybrid aerogels containing fibers of dual-scale sizes and knotty networks for tissue regeneration.

The structure and design flexibility of aerogels make them promising for soft tissue engineering, though they tend to come with brittleness and low elasticity. While increasing crosslinking density may improve mechanics, it also imparts brittleness. In soft tissue engineering, resilience against mechanical loads from mobile tissues is paramount. We report a hybrid aerogel that consists of self-reinforcing networks of micro- and nanofibers. Nanofiber segments physically entangle microfiber pillars, allowing efficient stress distribution through the intertwined fiber networks. We show that optimized hybrid aerogels have high specific tensile moduli (~1961.3 MPa cm3 g-1) and fracture energies (~7448.8 J m-2), while exhibiting super-elastic properties with rapid shape recovery (~1.8 s). We demonstrate that these aerogels induce rapid tissue ingrowth, extracellular matrix deposition, and neovascularization after subcutaneous implants in rats. Furthermore, we can apply them for engineering soft tissues via minimally invasive procedures, and hybrid aerogels can extend their versatility to become magnetically responsive or electrically conductive, enabling pressure sensing and actuation.