Crosslinking Density Research Articles

Shape memory and mechanical properties of ESO modified epoxy/polyurethane semi-interpenetrating polymer networks for smart plaster

While numerous studies have explored the potential of shape memory materials in medical applications, the current research output is not enough for significant productivity in industrial products. In this research, a type of shape memory orthopedic plaster was fabricated by using epoxy/polyurethane interpenetrating networks modified with epoxidized soybean oil (ESO) and then compared with some commercial plasters. Polymer networks that were produced could be tailored to have glass transition temperatures (Tgs) within the range of 70–90 °C by changing the percentage composition of polyurethane and soybean oil. Shape recovery and fixity ratios in all samples were above 95 and 97 %. DMA results showed that IPNs with variable amount of soybean oil had lower glass transition temperature (Tg) and cross-link densities compared to IPNs without soybean oil. Based on the tensile test results, most samples exhibited an elastic modulus in the range of 280–400MPa, a level deemed somewhat acceptable when compared to commercial samples. Light microscope images had shown that the increase of polyurethane led to the phase separation of polymers, which was improved by the addition of soybean oil.

Material Characterization of Silicones for Additive Manufacturing.

Three-dimensional printing is ideally suited to produce unique and complex shapes. In this study, the material properties of polysiloxanes, commonly named silicones, produced additively by two different methods, namely, multi-jet fusion (MJF) and material extrusion (ME) with liquid printing heads, are investigated. The chemical composition was compared via Fourier-transform infrared spectroscopy, evolved gas analysis mass spectrometry, pyrolysis gas chromatography coupled to mass spectrometry, and thermogravimetry (TGA). Density and low-temperature flexibility, mechanical properties and crosslink distance via freezing point depression were measured before and after post-treatment at elevated temperatures. The results show significant differences in the chemical composition, material properties, as well as surface quality of the tested products produced by the two manufacturing routes. Chemical analysis indicates that the investigated MJF materials contain acrylate moieties, possibly isobornyl acrylate linking branches. The hardness of the MJF samples is associated with crosslinking density. In the ashes after TGA, traces of phosphorus were found, which could originate from initiators or catalysts of the curing process. The ME materials contain fillers, most probably silica, that differ in their amount. It is possible that silica also plays a role in the processing to stabilize the extrusion strand. For the harder material, a higher crosslink density was found, which was supported also by the other tested properties. The MJF samples have smooth surfaces, while the ME samples show grooved surface structures typical for the material extrusion process. Post-treatment did not improve the material properties. In the MJF samples, significant color changes were observed.

Comprehensive Characterization of Drying Oil Oxidation and Polymerization Using Time-Resolved Infrared Spectroscopy.

Drying oils like linseed oil are composed of multifunctional triglyceride molecules that can cure through three-dimensional free-radical polymerization into complex polymer networks. In the context of oil paint conservation, it is important to understand how factors like paint composition and curing conditions affect the chemistry and network structure of the oil polymer network and subsequently the links between the structure and long-term paint stability. Here, we employed time-resolved ATR-FTIR spectroscopy and comprehensive data analysis to study the curing behavior of five types of drying oil and the effects of curing temperature as well as the presence of a curing catalyst (PbO). Extracted concentration curves of key reactive functional groups point to a phase transition similar to a gel point that is especially pronounced in the presence of PbO, after which curing reactivity slows down dramatically. Analysis of kinetic parameters suggests that PbO induces a network structure with a more heterogeneous cross-link density, and the ATR-FTIR spectra indicate lower levels of oxidation in those cases. Finally, lower temperatures appear to favor the formation of carboxylic acid groups in oil mixtures with PbO.

Impact of Annealing Chemistry on the Properties and Performance of Microporous Annealed Particle Hydrogels.

Microporous annealed particle (MAP) hydrogels are a promising class of in situ-forming scaffolds for tissue repair and regeneration. While an expansive toolkit of annealing chemistries has been described, the effects of different annealing chemistries on MAP hydrogel properties and performance have not been studied. In this study, we address this gap through a controlled head-to-head comparison of poly(ethylene glycol) (PEG)-based MAP hydrogels that were annealed using tetrazine-norbornene and thiol-norbornene click chemistry. Characterization of material properties revealed that tetrazine click annealing significantly increases MAP hydrogel shear storage modulus and results in slower in vitro degradation kinetics when microgels with a higher cross-link density are used. However, these effects are muted when the MAP hydrogels are fabricated from microgels with a lower cross-link density. In contrast, in vivo testing in murine critical-sized calvarial defects revealed that these differences in physicochemical properties do not translate to differences in bone volume or calvarial defect healing when growth-factor-loaded MAP hydrogel scaffolds are implanted into mouse calvarial defects. Nonetheless, the impact of tetrazine click annealing could be important in other applications and should be investigated further.

Coupled field modeling of thermoresponsive hydrogels with upper/lower critical solution temperature

An inf–sup stable FE formulation for the thermo-chemo-mechanical simulation of thermoresponsive hydrogels is herein proposed by approximating the displacement field via quadratic shape functions and both the chemical potential (fluid pressure) and the temperature fields by linear functions. The formulation is implemented into a stable thermo-chemo-mechanical user-element subroutine (UEL) in Abaqus, denoted as Q2Q1Q1. The proposed formulation has been validated in relation to thermoresponsive hydrogels to interpret several examples of transient diffusion-driven swelling deformations. First, the upper/lower critical solution temperature behaviors of thermoresponsive hydrogels has been captured, studying several peculiarities comprising the diffusion length influence at the instantaneous loading state and the overlooked influence of the mass flux and the hyperelastic stretching on the temperature field. Subsequently, numerical analysis have been conducted in order to investigate the impact of temperature-dependent swelling ratio on the mechanical behavior of spheres undergoing compression. The accuracy of the proposed formulation has been assessed by numerically replicating the seminal experiments that explore the influence of crosslinking density on the thermally driven swelling of PNIPAAm hydrogels.

Anti-corrosion design of layered zirconium-based metal–organic frameworks (Zr-MOF) enhanced epoxy nanocomposite coatings

In this work, two-dimensional UiO-67 nanosheets are successfully modified on graphene oxide (GO). The synthesized GO@2D-UiO-67 composite not only exhibits the electrical insulation characteristics of Zr-MOF, but also leverages the passive barrier effect of its 2D layered structure to prepare a highly anticorrosive epoxy coating. Electrochemical measurements reveal that the impedance modulus of the GO@UiO-67/EP composite coating remain two orders of magnitude higher than that of the pure EP coating even after 28 days of immersion in 3.5 wt% NaCl solution. This good long-term anti-corrosion performance could derive from the enhanced crosslinking density of composite coating due to the incorporation of GO@UiO-67 nanosheets. Furthermore, the shielding effect of layered structure and the corrosion inhibition behavior of organic ligands are proved to improve the corrosion resistance properties of composite coating. This research fills the application void of two-dimensional Zr-MOF composites in resin coatings, as well as serves as a forward-looking initiative to enhance the long-term corrosion protection of epoxy resin coatings.

Co-regulation of gelatin content and Hofmeister effect on 3D-printed high internal phase emulsion gel characteristics for resveratrol delivery

The study investigated the influence of gelatin (GE) content and the Hofmeister effect on the physicochemical, rheological, and printing properties of high internal phase emulsion (HIPE) gels. Incremental GE content introduced more triple helix structures (junction zones) in the continuous phase of HIPE. By soaking in a sodium citrate (Na3Cit)-glycerol-water solution, polymer chain bundling, hydrophobic interactions, and abundant hydrogen bonds between GE and glycerol further increased, achieving a more compact crosslinking density and internal network. The optimized HIPE-GE-Cit3- gel with 1.5 wt% GE displayed improved shape retention, generating smoother and firmer gels with enhanced freezing and heat resistance. Its excellent mechanical strength and viscoelasticity can resist large deformations and maintain reversible structures. HIPE-GE gel with 1.5 wt% GE demonstrated satisfactory printing suitability with clear outlines, favorable visual aesthetics, and minimal dimensional deviation. This post-soaking (Hofmeister effect) also eliminated rough surfaces and visible layered lines, improved mechanical properties and more elastic networks. The printed HIPE-GE1.5-Cit3- gel with higher rigidity and elasticity impeding molecular release, protected encapsulated resveratrol against degradation, especially from heat, and enhanced the release rate in the small intestine, achieving sustained release. This work produced customizable HIPE gels by 3D printing with multiple advantages to develop personalized nutraceutical carriers with high-temperature tolerance.

Design of hybrid multi-crosslinked hydrogel with a combination of high stiffness, elastic applied in high temperature and high salinity reservoirs

The mechanical strength of conventional hydrogels is inadequate for preventing leakage in high-temperature and high-salinity reservoirs, primarily due to the increased mobility of polymer chains and the degradation of crosslinked networks. Herein, we employed the strategy of ’network nesting and layer reinforcement’ to design a hybrid multi-site crosslinked hydrogel. This approach enhances the interconnections between polymer chains and fortifies the crosslinked network. The shear rheological behavior and temperature sensitive characteristics of the profile control working fluids were evaluated based on rheological dynamics. In the high temperature (140 ℃) and high salinity (21.81 × 104 mg/L) preparation environment, the effects of different components to the mechanical strength of the hydrogel were investigated under dynamic shear and uniaxial compression conditions. The incorporation of N-(hydroxymethyl)acrylamide (NMA) in the copolymerization with acrylamide (AM) resulted in an increase in the covalent cross-linking density, leading to a rise in the shear elastic modulus from 105 Pa to 238 Pa. The use of pre-gelatinized cassava starch (PGCM) as the grafting framework enhanced the bonding between the polymer chains, as evidenced by the increase in uniaxial compressive strength from 0.018 MPa to 0.081 MPa and the rise in peak strain from 55.0 % to 72.9 %. Furthermore, the synergistic effect of fumed silica (AEROSIL), which exploits mechanical coupling between inorganic nano-fillers and organic polymers, increased the compressive strength from 0.081 MPa to 0.418 MPa and raised the peak strain from 72.9 % to 81.8 %. It provides an effective approach to enhance the plugging performance of hydrogels in high temperature and high salinity reservoirs.

Bio-derived Schiff base vitrimer with outstanding flame retardancy, toughness, antibacterial, dielectric and recycling properties

Thermosetting resins are widely used in high-tech applications for excellent mechanical robustness and chemical resistance. With increasing attention to the environmental and usage safety issues, it is necessary to develop bio-derived, recyclable, tough, and fire-retardant thermosetting resins. Herein, a high-performance, vanillin-based vitrimer (CIP1.0) was prepared. The CIP1.0 with 1.0 wt% phosphorus passes vertical burning (UL-94) V-0 rating with a limiting oxygen index (LOI) of 27.2%. The phosphorus-containing and Schiff base groups act synergistically in gas and condensed phases during combustion, endowing CIP1.0 with outstanding fire retardancy. The CIP1.0 shows excellent toughness with high elongation at break of 45.0% due to the π-π stacking of numerous rigid aromatic groups and appropriate cross-linking density. The highly symmetrical structure and low polarizability of CIP1.0 result in a low dielectric constant. The CIP1.0 exhibits superior antimicrobial properties. The CIP1.0 can be reprocessed by hot-pressing at 140 °C for 10 min. The non-destructive, closed-loop recycling of carbon fibers in the carbon fiber-reinforced CIP1.0 composite can be achieved under mild conditions due to the degradable Schiff base groups of CIP1.0. In this work, a bio-derived, tough, fire-retardant, low dielectric, and antimicrobial vitrimer is prepared to provide a rational strategy for the design of advanced environmentally friendly thermosetting resins.

In-situ halloysite functionalization of anionic hybrid gels possessing easily implemented site-specific (alkyl)amide and carboxyl groups

Design of functional materials with tunable properties based on anionically-modified copolymer network of poly (N-isopropyl acrylamide-co-methacrylic acid) P(NIPA-co-MA) containing linear polyacrylamide and various amounts of Halloysite nanotubes (Hal) was presented using a facile route of solution casting. The organic/inorganic nanostructures based on thermo-responsive PNIPA were constructed to create hybrid materials via in situ polymerization with different Hal-loading and then used for the removal of cationic methylene blue (MB) dye from aqueous solutions. To achieve the desired mechanical property, the optimum composition of hybrids was determined following a simple and cost-effective synthesis procedure. In situ one-pot polymerization was promoted by semi-IPN formation, following a much simpler route than traditional preparation approaches for stable cross-linked hybrid formation. The swelling of hybrids decreased by 2.9-fold with loading of 5.40 % Hal, confirming the hydrogen bonding interactions between Hal and PAAm/P(NIPA-co-MA) network. The mechanical properties of Hal-doped hybrid gels showed an increase–decrease tendency with increase of Hal-content from 0.80 to 5.40 % (w/v) due to the high aspect ratio of Hal and strong secondary interactions between Hal and PAAm/P(NIPA-co-MA) chains. The effective cross-link density for Hal-doped hybrids was expressed by a cubic polynomial as a function of Hal concentration. Temperature-sensitive swelling results showed that the advantage of sustained release property of Hal can be combined with excellent controllability of PNIPA-based network. Adsorption results of MB onto Hal-doped hybrids bearing methacrylic acid moieties demonstrated their potential as efficient adsorbents for the removal of cationic dyes. A new route offered by the proposed procedure for design of hybrids containing “green” one-dimensional nanofillers creates an innovative perspective on robust hybrid structures for practical applications.

Facile Preparation of Irradiated Poly(vinyl alcohol)/Cellulose Nanofiber Hydrogels with Ultrahigh Mechanical Properties for Artificial Joint Cartilage.

In this study, Poly(vinyl alcohol)/cellulose nanofiber (PVA/CNF) hydrogels have been successfully prepared using γ-ray irradiation, annealing, and rehydration processes. In addition, the effects of CNF content and annealing methods on the hydrogel properties, including gel fraction, micromorphology, crystallinity, swelling behavior, and tensile and friction properties, are investigated. Consequently, the results show that at an absorbed dose of 30 kGy, the increase in CNF content increases the gel fraction, tensile strength, and elongation at break of irradiated PVA/CNF hydrogels, but decreases the water absorption. In addition, the cross-linking density of the PVA/CNF hydrogels is significantly increased at an annealing temperature of 80 °C, which leads to the transition of the cross-sectional micromorphology from porous networks to smooth planes. For the PVA/CNF hydrogel with a CNF content of 0.6%, the crystallinity increases from 19.9% to 25.8% after tensile annealing of 30% compared to the original composite hydrogel. The tensile strength is substantially increased from 65.5 kPa to 21.2 MPa, and the modulus of elasticity reaches 4.2 MPa. Furthermore, it shows an extremely low coefficient of friction (0.075), which suggests that it has the potential to be applied as a material for artificial joint cartilage.

A novel UV-curable composite coating with superior anti-corrosion and mechanical properties

The UV curing method is free from volatile organic compounds (VOC) and exhibits high curing efficiency. However, pore flaws and inadequate mechanical qualities after cure greatly hinder their utilization in metal anti-corrosion. Herein, layered double hydroxides (LDH) supported by molybdic acid and cerium ions were synthesized in situ on the sericite (SC) surface, enhancing the shielding, corrosion inhibition, resin compatibility, and cross-linking density of the coating. Compared with carbon steel immersed in a 3.5 wt% NaCl solution, the incorporation of SC/KH560@LDH reduced the corrosion current density (Icorr) from 2.001 × 10−5 A/cm2 to 7.883 × 10−6 A/cm2. Moreover, the low-frequency impedance of the UV-SC/KH560@LDH coating remained high at 1.939 × 1010 Ω·cm2 after 70 days of immersion in a 3.5 wt% NaCl solution. The excellent corrosion resistance of UV-SC/KH560@LDH can be attributed to the barrier properties of the filler, the chloride ion trapping, and the passivation effect. Furthermore, the UV-curable alkyd resin used in this work formed a chemical bond with the metal substrate, enhancing the mechanical properties of the coating. The adhesion strength of the UV-SC/KH560@LDH was measured at 11.50 MPa. The thickness loss (21.3 μm) of the UV-SC/KH560@LDH were minimal after 5000 cycles of wear. A new research concept for preparing the UV-SC/KH560@LDH with superior anti-corrosion and mechanical properties for carbon steel plate surfaces has been proposed to meet the demands of practical applications.

Modular design of Diels-Alder reversible networks for the facile production of highly tunable materials

Covalent adaptable networks (CANs) have attracted significant attention due to their potential to form crosslinked, yet reprocessable networks. Their ability to rearrange upon exposure to specific stimuli, in combination with properties such as self-healing can advance the development of novel materials, including for additive manufacturing. Thorough understanding of structure-property relations and processing potential will aid future application-driven research in network design as well as material selection. Therefore, a multitude of CANs were synthesized herein, by crosslinking epoxide-based oligomers via the furan-maleimide Diels-Alder reaction, to evaluate small systematic variations of (co)monomer composition, crosslinker length/flexibility and crosslinking density as vectors of tuning the CANs' thermomechanical properties. Networks with glass transition temperatures (Tg) spanning from <−40 °C up to >20 °C and Young's Moduli spanning from 0.2 MPa to >500 MPa were readily attainable. Crosslinker length/flexibility had a profound impact on the tensile properties, while changes in backbone composition provided insight into the impact of secondary interactions versus rigid moieties on mechanical performance. Self-healing at ambient conditions was demonstrated for elastomeric networks, with healing efficiency being enhanced when using longer crosslinkers. Finally, a cell viability and metabolic activity assay provided a preliminary in vitro demonstration of the biocompatibility of these materials.

Siloxane-containing epoxy resins derived from magnolol with low dielectric properties, excellent toughness, and flame retardancy

The entanglement disorder, highly polar groups and carbon-rich structure of conventional epoxy resins result in high dielectric constants and flammability, posing challenges to the development of high-frequency communications. Therefore, a silicone-containing active ester curing agent (FMAE) derived from magnolol was synthesized via a straightforward two-step process. And a thermosetting resin (FMAE/TGDDM) was then obtained by moisture self-cross-linking as well as curing epoxy N, N, N, N-tetraethoxypropyl-4, 4-diaminodiphenylmethane (TGDDM). The epoxy resin (MAE/TGDDM) cured by MAE that was not undergoing click chemistry was used for comparison. The results showed that the large volume of curing agents (31.86 Å × 14.98 Å × 9.03 Å for FMAE, 16.01 Å × 11.46 Å × 8.09 Å for MAE) and the absence of –OH enabled both resins to have excellent dielectric properties, especially FMAE/TGDDM, with a Dk of 2.78 and a Df of 0.0066 at 10 MHz. Additionally, FMAE/TGDDM demonstrated favorable impact resistance (43.9 kJ/m2) and lower hygroscopicity (0.56%) than MAE/TGDDM, which due to the introduction of siloxane chain (Si% = 7.08%) and the increase of the crosslinking density (2302 mol/cm3 vs 6751 mol/cm3). Furthermore, the charring rate of FMAE/TGDDM was 39.1%, almost twice that of MAE/TGDDM, and the PHHR and THR were 201.2 W/g and 22.6 kJ/g, 103.9% and 67.7% lower than MAE/TGDDM, respectively, proving that the intrinsic flame retardancy of FMAE/TGDDM. Hence, this paper provides a strategy to synergistically address the limitations of TGDDM and conventional epoxy resins for impact resistance, dielectric properties and flame retardancy through a simple structural design.

Computer Simulations of Responsive Nanogels at Lipid Membrane.

The swelling and collapse of responsive nanogels on a planar lipid bilayer are studied by means of mesoscopic computer simulations. The effects of molecular weight, cross-linking density, and adhesion strength are examined. The conditions for collapse-mediated engulfing by the bilayer are found. In particular, the results show that at low hydrophobicity level the increase in the nanogel softness decreases the engulfing rate. On the contrary, for stronger hydrophobicity level the trend changes to the opposite one. At the same time, when the cross-linking density is too low or the adhesion strength is too high the nanogel deformation at the membrane suppresses the engulfing regardless of the network swelling ratio. Finally, for comparative reasons, the behavior of the nanogels is also studied at the solid surface. These results may be useful in the design of soft particles capable of tuning of their elasticity and porosity for successful intracellular drug delivery.

Programmable bionanocomposite coated fertilizers for prolonged controlled release of nitrogen

Controlled-release fertilizers (CRFs) present a promising solution for alleviating food and nutrient scarcity. However, their development has been mainly hindered by both rapid and unsynchronized nutrient release and unsustainable coating materials. In this study, we address this issue by developing a new coating layer for CRFs using a programmable biopolyurethane nanocomposite. This nanocomposite is prepared from diphenylmethane diisocyanate (MDI)-functionalized bentonite nanoclay (BNT-MDI) and a biopolyol from biomass waste. The results show that the BNT-MDI-doped CRFs (BCRFs) exhibit an impressive nitrogen (N)-release longevity of approximately 120 days at a 4 wt% coating ratio, surpassing previous CRF formulations. In a 30-day snap bean cultivation study, BCRF significantly improved root length (1000 %), leaf length (257 %), leaf width (400 %), and plant height (1400 %) compared to the control. The superior performance of BCRF is attributed to the PU-nanoclay biocomposite film, with full nano-exfoliation, controllable porosity, and high crosslinking density. Furthermore, we introduce a new dynamic release mechanism and establish a quantitative relationship between the nanostructure, property, and release performance of BCRF by combining the multiplicative and diffusion models for porous materials. This study provides a theoretical framework and a straightforward methodology for designing programmable nanocomposite structures for future biobased CRFs.

Structural effects on heat capacity, moisture absorption and thermal expansion of epoxy-novolac polymers

Today epoxy novolac resins are of great interest for the aerospace industry. Thermal properties of the polymer matrix, as well as the effect of moisture on the characteristics of polymer composite materials (PCM) under thermomechanical impacts, are critical tasks in creating dimensionally stable structures operating in a wide temperature range. Particularly, thermal and moisture expansion as well as heat capacity are important parameters for evaluating of polymer matrices and modeling their properties. In this work, polymers based on a number of epoxy novolac resins with aromatic amine hardener were studied. The values of the crosslink density were experimentally determined, and a comparative analysis of thermal expansion and heat capacity for epoxy polymers with different crosslink density was carried out. The dependence of thermophysical properties on polymer crosslinking density is shown, both in glass and highly elastic states. Additionally, this study analyzes the process of water sorption by polymers and the coefficient of moisture expansion. The most significant dependence of the diffusion coefficient was observed with coefficient of moisture expansion.

Modulation of Mechanical Properties of Silica-Filled Silicone Rubber by Cross-Linked Network Structure.

Associating molecular structure and mechanical properties is important for silicone rubber design. Although silicone rubbers are widely used due to their odourless, non-toxic, and high- and low-temperature resistance advantages, their application and development are still limited by their poor mechanical properties. The mechanical properties of silicone rubbers can be regulated by designing the cross-link density and cross-linking structure, and altering the molar contents of vinyl in the side groups of methyl vinyl silicone rubber (MVQ) leads to different cross-linking structures and cross-linking densities in the vulcanized rubber. Therefore, this study investigated the differences in molecular parameters and molecular chain structures of unprocessed MVQ rubbers with different vinyl contents. The results showed that MVQ rubbers with high vinyl contents were branched polymers, better facilitating the cross-linking reaction than MVQ rubbers with low vinyl contents. In addition, silicone rubbers with different vinyl contents were co-cross-linked to introduce an inhomogeneous cross-linked network in the silicone rubber to improve its mechanical properties. The cross-linked network properties were analysed by the Flory-Rehner model and Mooney-Rivlin plots, and it was found that the long chains in the sparsely cross-linked domains of the network favoured high elongation at break and the short chains in the densely cross-linked domains contributed to high modulus, which could satisfy the functions of reinforcing and toughening the rubber materials at the same time. It was also found by analysing the filler network and aggregate morphology that the inhomogeneous cross-linked network led to an improvement in the dispersion of silica in the rubber and a significant improvement in the mechanical properties of silicone rubber.

Sub-10 μm Soft Interlayers Integrating Patterned Multivalent Biomolecular Binding Environments.

Designing surfaces that enable controlled presentation of multivalent ligand clusters (e.g., for rapid screening of biomolecular binding constants or design of artificial extracellular matrices) is a cross-cutting challenge in materials and interfacial chemistry. Existing approaches frequently rely on complex building blocks or scaffolds and are often specific to individual substrate chemistries. Thus, an interlayer chemistry that enabled efficient nanometer-scale patterning on a transferrable layer and subsequent integration with other classes of materials could substantially broaden the scope of surfaces available for sensors and wearable electronics. Recently, we have shown that it is possible to assemble nanometer-resolution chemical patterns on substrates including graphite, use diacetylene polymerization to lock the molecular pattern together, and then covalently transfer the pattern to amorphous materials (e.g., polydimethylsiloxane, PDMS), which would not natively enable high degrees of control over ligand presentation. Here, we develop a low-viscosity PDMS formulation that generates very thin films (<10 μm) with dense cross-linking, enabling high-efficiency surface functionalization with polydiacetylene arrays displaying carbohydrates and other functional groups (up to 10-fold greater than other soft materials we have used previously) on very thin films that can be integrated with other materials (e.g., glass and soft materials) to enable a highly controlled multivalent ligand display. We use swelling and other characterization methods to relate surface functionalization efficiency to the average distance between cross-links in the PDMS, developing design principles that can be used to create even thinner transfer layers. In the context of this work, we apply this approach using precision glycopolymers presenting structured arrays of N-acetyl glucosamine ligands for lectin binding assays. More broadly, this interlayer approach lays groundwork for designing surface layers for the presentation of ligand clusters on soft materials for applications including wearable electronics and artificial extracellular matrix.

Fabricating epoxy vitrimer with excellent mechanical and dynamic exchange properties via network topology design

Epoxy vitrimers are a novel type of environmentally friendly materials that possess exceptional properties, including self-healing, recyclability, and reprocessability. They offer a solution to the issue of traditional thermosetting epoxy resins, which are not recyclable. However, the incorporation of dynamic bonds typically results in a decrease in mechanical properties. Therefore, achieving a balance between the mechanical properties and dynamic exchange capability is crucial. In this work, a series of epoxy resin systems with various topological network characteristics were prepared by adjusting the proportions of bisphenol A epoxy resin (E51) and polyethylene glycol diglycidyl ether (EGDGE) epoxy resins in combination with a curing agent containing vinylogous urethane (VU) dynamic bonds. Through further study, we found that with the increase of E51 content, the cross-linking density of the network gradually increased, and the flexibility of the macromolecular chains decreased (favorable for enhancing the material's mechanical performance). Simultaneously, the free volume of the network gradually increased, and the tightness of the macromolecular chains decreased (favorable for improving the material's dynamic exchange ability). These two effects combined to make E51-40 exhibit the lowest activation energy for dynamic covalent bond exchange and the lowest topological transition temperature. Compared to E51-0, the tensile strength and glass transition temperature of E51-40 were improved by 22.23 % and 25.30 %, respectively. After remoulding experiment at 140 °C for 1h, the material exhibited a high tensile strength recovery of 91.34 %. Therefore, starting from the design of molecular structure, adjusting the network topology is an effective means to balance the mechanical and dynamic exchange properties of epoxy vitrimers. This provides experimental guidance and theoretical insights for designing high-performance epoxy vitrimer materials.