Crosslinking Density Research Articles

Elastocaloric Performance of Natural Rubber in Solid State Cooling: Evaluation of the Effect of Crosslinking Density

Elastocaloric cooling is recognized as a promising alternative to modern vapor-compression cooling systems, which often rely on environmentally hazardous refrigerants. Natural rubber (NR), a well-known renewable resource, stands out among elastomers exhibiting elastocaloric behavior due to a peculiar combination of nontoxicity, low cost, softness, long-life fatigue and high caloric power. Despite these properties, research on the refrigeration potential of NR is still in its early stages, and several aspects require attention. This work investigates, for the first time, the effect of crosslinking density on the elastocaloric properties of NR. Samples with three different crosslinking densities (2.9, 4.0 and 5.2 mol·10−4/cm3) were produced by internal compounding and hot pressing, and thermo-mechanically characterized. The assessment of the elastocaloric effect of the produced samples revealed that reducing the crosslinking degree significantly enhanced the elastocaloric properties. To compare the cooling capacity of the samples, a qualitative coefficient of performance (COPmat) was evaluated as the ratio between extracted thermal energy and deformational work per unit volume. The results highlight that the least crosslinked sample achieved the higher COPmat, equal to 2.4. These results underscore the significance of crosslinking density as one of the primary factors to be considered to enhance the refrigeration potential of NR.

The Photocleavable Protein PhoCl-Based Dynamic Hydrogels.

Dynamic protein hydrogels have attracted increasing attention owing to their tunable physiochemical and mechanical properties, customized functionality, and biocompatibility. Among the different types of dynamic hydrogels, photoresponsive hydrogels are of particular interest. Here, we report the engineering of a photoresponsive protein hydrogel by using the photocleavable protein PhoCl. We employed the well-developed SpyTag and SpyCatcher chemistry to engineer PhoCl-containing covalently cross-linked hydrogels. In the hydrogel network, PhoCl, which can be cleaved into two fragments upon violet irradiation, is employed as a dynamic structural motif to regulate the cross-linking density of the hydrogel network. The resultant PhoCl-containing hydrogels showed photoresponsive viscoelastic properties. Upon violet irradiation, the PhoCl hydrogels soften, leading to an irreversible reduction in the storage moduli. However, no gel-sol transition was observed. Leveraging this light-induced stiffness change, we employed this hydrogel as a cell culture substrate to investigate the mechanobiological response of NIH-3T3 fibroblast cells. Our results showed that 3T3 cells can change their morphologies in response to the stiffness change of the PhoCl hydrogel substrate dynamically, rendering PhoCl-based hydrogels a useful substrate for other mechanobiological studies.

Circular Cross-Linked Polyethylene Enabled by In-Chain Ketones.

Cross-linked polyethylenes (PEs) are widely employed, but the permanent links between the chains impede recycling. We show that via imine formation with diamines keto-functionalized polyethylenes from both free-radical (keto-low-density PE, keto-LDPE) and catalytic (keto-high-density PE, keto-HDPE) nonalternating ethylene-CO copolymerization can be cross-linked efficiently in the melt, resulting in gel fractions of the formed cross-linked PEs of up to 85% and improved tensile properties. The imine-based cross-links in the material can be hydrolyzed at 140 °C to recycle up to 97% of the initial thermoplastic keto-polyethylene. Low keto contents of ≤1.5 mol % are found ideal to retain PE-like thermal properties, achieve sufficient cross-link density, and maintain circular recyclability.

Effect of Cross-Linking Density of Powdered Rubber on Gas Barrier Property and CO2 Permselectivity of NR/BR Composites

Effect of Cross-Linking Density of Powdered Rubber on Gas Barrier Property and CO2 Permselectivity of NR/BR Composites

Regulation of Glass Transition Temperature in Thermo‐Responsive Epoxy Shape Memory Polymers: The Roles of Chemical Crosslinking Density and Chain Flexibility

ABSTRACTShape memory polymers (SMPs) are novel kinds of smart materials whose shape can be changed in external conditions such as heat stimulus. Due to their excellent structural versatility and high elastic strain, they have important applications in the field of biomaterials. Here, a series of amorphous shape memory polymer materials are prepared and their shape memory properties and glass transition temperature (Tg) are also investigated. A special kind of epoxy polymer, whose shape can be changed at around physiological temperature, is synthesized by regulating the crosslinking density and introducing flexible aliphatic epoxy chains. The shape memory function of this epoxy polymer is studied by deformation test. In addition, to explore their application in the field of biomedical materials, the biocompatibility of the materials are evaluated, including the effects on the erythrocyte hemolysis rate and cell activity. The experimental results show that this kind of epoxy polymer has good shape memory function and biocompatibility.

The Modulation of Cross-Linking Density in Gel Polymer Electrolyte for the Inhibition of Lithium Dendrite

The Modulation of Cross-Linking Density in Gel Polymer Electrolyte for the Inhibition of Lithium Dendrite

Fabrication and Enhanced Flexibility of Starch-Based Cross-Linked Films.

The development of sustainable materials has driven significant interest in starch as a renewable and biodegradable polymer. However, the inherent brittleness, hydrophilicity, and lack of thermoplasticity of native starch limit its application in material science. This study addresses the limitations of native starch by converting it to dialdehyde starch (DAS) and cross-linking with polyether diamines via imine bonds. The effects of Jeffamine molecular weights (D-2000, D-400, and D-230) and mole ratios on the mechanical, thermal, and structural properties of starch-based films were examined. The cross-linked DAS/Js films exhibited significant enhancements in flexibility and toughness. Specifically, DAS/J2000 at a 0.03 mol ratio achieved a tensile strength of 62.9 MPa. In comparison, DAS/J400 at a 0.5 mol ratio demonstrated 126.2% elongation at break, indicating the balance between cross-linking density and chain mobility. X-ray diffraction (XRD) analysis revealed reduced crystallinity and tighter molecular packing with increased cross-linking. Dynamic mechanical analysis (DMA) indicated a decrease in Tg with an increasing mole ratio, reflecting enhanced molecular mobility. The results underscore the potential of optimized cross-linking conditions to produce starch-based films with properties that contribute to developing sustainable biopolymer materials.

Influence of hydrogen bonding interactions, entanglement, and covalent crosslinking on the viscoelasticity of acrylic viscoelastomers containing urea group

The structure–property relationship of acrylic clear viscoelastomer films (acrylic CVFs) as foldable optical clear adhesives (OCAs) has always been unclear. In our work, a series of acrylic CVFs with different hydrogen-bonding interactions (H-bondings) and cross-linking densities (namely, CL-H-copolymers) were synthesized. The effects of entanglement, H-bonding, and covalent crosslinking on the recovery and adhesive properties of CL-H copolymers were analyzed by rheology, equilibrium swelling, and tensile stress–strain tests (tensile tests). The structural parameter Mx/MeH was obtained by combining the affine deformation model, the Flory-Rehner equation, and the UCM-Gent model, where Mx is the molecular weight between covalent crosslinkers and MeH is the a physical crosslinking molecular weight affected by H-bondings. The experimental results showed that the CL-H-copolymers had an obvious dependence on Mx/MeH. Recovery properties tended to stabilize (>90 %) at Mx/MeH < 1, while adhesion strengths continued to decrease with decreasing Mx/MeH. This conclusion and methodology are instructive for the design of foldable OCAs with high elasticity and high adhesion performance.

Correlation between structural modifications and physical parameters of Sb doped InSe alloys for optoelectronic applications

Bulk samples of In0.1Se0.9-xSbx (0 ≤ x ≤ 0.24) were synthesized using the conventional melt-quenching technique. The impact of Sb doping on the structural and physical properties of InSe alloys was systematically explored. The substitution of Sb at the expense of Se introduces defects and dislocations in the lattice, which significantly influence the properties of the InSeSb system. With increasing Sb content, physical parameters such as the average coordination number, cross-linking density, mean bond energy, and cohesive energy were observed to increase. Theoretically calculated band gap values lie between 1.7 and 1.3 eV. X-ray diffraction (XRD) analysis confirmed the polycrystalline nature of the alloys, revealing the coexistence of rhombohedral α-In2Se3 and orthorhombic Sb2Se3 phases. Energy dispersive X-ray spectroscopy (EDX) confirmed the elemental composition, showing the presence of In, Se, and Sb in the bulk samples. Raman and FTIR spectroscopy further validated the presence of distinct structural units and molecular bonds as a function of Sb content, confirming the coexistence of α-In2Se3 and Sb2Se3 phases alongside In–Se, Se–Se, and Sb–Se bonds. A strong correlation was established between the experimental findings and theoretically calculated parameters, including the average coordination number, mean bond energy, glass transition temperature, cohesive energy, and optical band gap. This study provides a comprehensive insight into the compositional dependence of structural and physical properties in InSeSb chalcogenide alloys, enhancing our understanding of their potential applications.

The role of multivalent cations in determining the cross-linking affinity of alginate hydrogels: A combined experimental and modeling study

This study explores the development of a comprehensive mathematical model to predict the cross-link density of alginate hydrogels using varying concentrations of divalent and trivalent ions. By systematically investigating the effects of Ca²⁺, Ba²⁺, Cu²⁺, Sr²⁺, Mg²⁺, Fe3⁺ and Al³⁺, the research describes the relationship between ion concentration and cross-link density. Experimental data reveals that the type and concentration of these ions critically influence the mechanical properties of the resulting hydrogels, with trivalent ions such as Fe³⁺ forming stronger, triple cross-links that significantly enhance the hydrogel's mechanical strength. Among the divalent ions, the trend in binding affinity is as follows: Ba²⁺ with the highest affinity followed by Sr²⁺, Ca²⁺ and Cu²⁺, while Mg²⁺ stands out with the lowest affinity, significantly differing from the others. The deviation of Cu²⁺ (transition metal ion) from the expected trend in ion interactions suggests that coordination chemistry, along with ionic radius, valence, and cation coordination abilities, plays a significant role in determining interaction strength with alginate. The proposed model, enhanced with fitting parameters k1 and k2 to account for ion-specific effects, leverages the unique binding affinities and coordination chemistry of each ion to tailor alginate hydrogels for specific applications. The parameter k1 reflects the affinity of the ions for the alginate chains, while k2 captures the coordination abilities and cross-linking efficiency. This work not only advances the understanding of ion-mediated cross-linking in alginate systems but also offers a valuable tool for the design and optimization of hydrogels with precise mechanical properties governed by various applications.

Ferric ions crosslinked hyaluronic acid beads: potentials for drug delivery use

Introduction and purpose Despite the attractive properties of hyaluronic acid (HA), The preparation of HA beads is still challenging. This article reports the preparation of pH-sensitive gel HA beads. The ionic gelation method was used to prepare the HA gel beads using ferric ions. This cross-linking type is based on forming coordination bonds, which enhance the mechanical properties of the prepared beads. Methods The developed beads were characterized using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) examined the bead’s morphology. Furthermore, the potential of HA gel beads as an oral drug delivery system was investigated using metformin as a hydrophilic model drug. The entrapment efficiency and in vitro, release, and release kinetics were evaluated. The crosslinking density and HA concentration effect on drug release and bead swelling capacity under pH 1.2 and 7.4 were also investigated. Results The entrapment efficiency of metformin in HA beads was found to be 79.56 ± 3.89%. FTIR analysis indicated the ionic interaction between ferric ions and the carboxylic groups on the HA molecule. At the same time, there was no substantial interaction between metformin and the polymeric bead. Morphological evaluation and DSC analysis suggested the successful incorporation of metformin within the beads. The in vitro drug release evaluation showed pH-dependent extended release where the release kinetics followed the first-order mathematical model. Conclusions This study provides a value-added formulation with the potential for drug delivery use, which can be further investigated for biomedical applications.

Enhancement of mechanical properties of natural rubber latex sheets by incorporating allyl-modified microcrystalline cellulose (AMCC)

Microcrystalline cellulose (MCC) was chemically modified with allyl bromide through the hydroxyl groups of cellulose to obtain allyl-modified microcrystalline cellulose (AMCC). To enhance the curing and mechanical properties of natural rubber latex, this AMCC was then compounded with a natural rubber latex formulation to produce rubber sheets. Unmodified MCC was also compounded and prepared into rubber sheets, which served as a reference. The formation of AMCC was confirmed using Fourier Transform Spectroscopy (FTIR). Furthermore, the thermal behavior of AMCC was examined by thermogravimetric analysis (TGA), and the degree of crystallinity before and after modification was evaluated by X-ray diffraction (XRD). The results of the rubber sheets showed that overall, maximum torque (MH), degree of crosslinking density, vulcanization rate (cure rate index), and tensile strength increased in AMCC-loaded rubber compared to MCC-loaded sheets. On the other hand, optimum cure time (t90) and elongation at break were lower in the AMCC-loaded rubber than in the MCC-loaded sheets. In overall, this method outlines a successful incorporation of modified cellulose into natural rubber-based products to obtain enhanced mechanical properties.

Effect of limited hydrolysis on the structure and gel properties of soybean isolate proteins: A comparative study of papain or/and trypsin

Plant protein's gelation is crucial in various food applications, and hydrolysis may enhance their gelation properties. In this study, we prepared soybean protein isolate hydrolysates (SPIH) using trypsin and/or papain, and found significant improvement in the solubility and gelling properties. These proteases broken down the peptide bonds and caused the exposure of hydrophobic groups as well as the unfolding of protein. Low molecular weight (<35 kDa) SPIHs were generated by the two-step enzymatic hydrolysis, showing significant improvements in storage modulus (G′), loss modulus (G″), viscosity, strength, and water-holding capacity (WHC). Among, PT-10 exhibited the highest WHC (61.72 ± 0.36 %), gel strength (4.67 ± 0.12 g), and network cross-linking density (0.33 ± 0.01 mol/m3), while its solubility was also significantly increased up to 254 %. According to the results of gel molecular force interactions, disulfide bonds, hydrophobic interactions and hydrogen bonds involved in the gel network formation. These findings reveal that the appropriate hydrolysis modification may improve SPI gel's properties and expand its application in gel foods.

Poroelastic fracture of polyacrylamide hydrogels: Enhanced crack tip swelling driven by chain scission

The deformation of hydrogels is accompanied by water migration, a process that plays a crucial role in their fracture behaviors. Previous investigations primarily focus on how the water migration between the environment and hydrogel affects the fracture of hydrogels. Herein, a novel mechanism of the rate-dependent fracture of hydrogels induced by interior water migration is uncovered. Notched polyacrylamide (PAAm) hydrogels are stretched at various stretch rates in both oil and deionized (DI) water environments. Notably, the critical stretches to crack propagation are positively correlated with the stretch rates in both the two environments. This rate-dependent fracture is attributed to the crack tip swelling of PAAm hydrogels. Delayed fracture tests conducted in oil further verify the co-existence of delayed fracture and rate-dependent fracture resulted from interior water migration in PAAm hydrogels. The experimental findings are interpreted by considering the imperfection of a real polymer network, in which the scission of short chains in the region neighboring the crack tip reduces the average crosslinking density locally, thereby greatly amplifying the degree of crack tip swelling and its influence on the fracture of hydrogels. A constitutive model coupling the evolution of polymer network and the diffusion of water molecules is proposed, which can predict the crack tip swelling of notched PAAm hydrogels through the finite element method. Assuming that the decrease in fracture toughness is positively related to the swelling along the crack propagation surface, the predicted normalized fracture toughness matches the experimental results of PAAm hydrogels stretched in water well, and satisfies those in oil environment qualitatively. This work highlights the significant influence of interior water migration on the fracture of hydrogels and provides insights that may guide the design of hydrogels with enhanced fracture resistance.

Effects of crosslinked rubber particles on rheological behaviors of ethylene-propylene-diene rubber/ polypropylene thermoplastic vulcanizates

A novel secondary vulcanization-dilution process was employed to prepare ethylene-propylene-diene rubber/polypropylene (EPDM/PP) thermoplastic vulcanizates (TPVs) with uniform size, controllable crosslinking density, and content of rubber particles to assess their significant impact on rheological behavior using Fourier-rheology, shedding light on the interplay between microstructural features and macroscopic material properties. Through the application of the time-concentration superposition principle, a broad reinforcement spectrum is established, enhancing the understanding of TPV structure-property relationships. Also studied is the Mullins effect of the TPVs at two different temperatures, contributing to a deeper understanding of their deformation mechanisms. The results offer valuable insights for the formulation and processing of TPVs, emphasizing the importance of tailored particle characteristics for optimizing material performance.

Tailoring structural and mechanical properties of konjac glucomannan/curdlan composite hydrogels by freeze-thaw treatment

To improve the gelling properties of konjac glucomannan/curdlan (KGM/CUD) composite hydrogels, KGM/CUD composite hydrogels were treated by freeze-thawing. Herein, we focus on the effects of freeze-thaw cycles, freezing temperature, and freezing time on the structural and mechanical properties of KGM/CUD composite hydrogels. SEM and SAXS results showed that ice crystals generated by freezing extruded the molecular chains and increased the cross-linking density between molecular chains, which resulted in a denser gel microstructure. Among them, the freeze-thaw treatment at −20 °C for 12 h can effectively reduce the correlation length (ξ). According to mechanical testing, freeze-thawed gels for 48 h reached 408-, 826-, and 840-fold of the hardness, gumminess and chewiness of unfrozen, respectively. After freeze-thaw treatment, the energy storage modulus (G') of the gel increased to 9872 Pa, the residual mass after heating was up to 27.9 %, the water holding capacity (WHC) was reduced to 80.85 %. In addition, low-field nuclear magnetic resonance results confirmed that the freeze-thaw treatment promoted the formation of ice crystals from water molecules, which realized the transition of the water state, thus reducing the water mobility of the gel. This study provides a facile and efficient strategy for designing hydrogels products with exceptional texture and sensory characteristics.

In-situ Forming Multipolymeric Glucose-Responsive Hydrogels.

Stimuli-responsive hydrogels (HGs) have shown promise for smart drug delivery applications. Specifically, glucose-responsive HGs having phenylboronic acid (PBA) functional groups are extensively pursued for insulin delivery in hyperglycemia. Current polymeric glucose-responsive HGs are cumbersome to fabricate and show a limited insulin release profile. Herein, we develop a straightforward fabrication of glucose-responsive multipolymer HGs (MPHGs) using a three-component in situ mixing. Molecular cargo, such as insulin, was loaded during the gelation. Heterobifunctional formylphenylboronic acid (FPBA) crosslinkers were used to interconnect polyvinyl alcohol (PVA) and branched polyethyleneimine (PEI) via boronate ester and imine bonds, respectively. Three positional isomers of FPBA (2FPBA, 3FPBA, and 4FPBA) resulted in HGs with distinct viscoelastic behaviors under the same conditions. HGs derived from 4FPBA exhibited more solid-like properties compared to 2FPBA and 3FPBA due to a higher crosslinking density. All the HGs exhibited glucose-responsive dissolution and release of embedded insulin cargo without disrupting the native structure. Insulin release profiles show a higher glucose-responsive release from 4FPBA-derived MPHGs. All the HGs were injectable, self-healing, and noncytotoxic below 10 μg/ml concentrations. The MPHGs developed in this study uncover new directions in creating glucose-responsive matrices for self-regulating drug delivery applications. In the future, detailed in vivo studies will be performed for clinical applications.

Experimental evaluation and simulation of myoblast cell alignment on the UV-irradiated liquid crystalline elastomers as a versatile tissue-engineered Scaffolding material

Efforts to develop versatile tissue-engineered scaffolds mimicking the functions of extracellular matrices (ECMs) have led to the emergence of liquid crystalline elastomers (LCEs) as promising materials. Here, thiol-acrylate-based LCEs forming a nematic phase upon UV irradiation were synthesized, and their biological compatibility was evaluated using C2C12 myoblast cells. Prior to UV exposure, some characteristics, e.g., phase transition temperature (TNI), order parameter, and reaction time, of the as-synthesized LCEs are characterized for property optimization. Fourier-transform infrared spectroscopy revealed that thiol-acrylate Michael addition polymerization was successful, judged by the disappearance of the characteristic peaks of thiol and acrylate groups. Differential scanning calorimetry thermograms and dynamic mechanical thermal analysis curves showed TNI values at ca. 49 °C, at which point the nematic phase is the dominant morphology. Moreover, the cross-linking density, the fixing, and the recovery ratios for the sample with optimal properties (i.e., LCE3) were determined to be 10.3 mol/cm3, 97.2 % and 91 %, respectively. Assessment of mesomorphism and roughness demonstrated the suitability of LCE3 for cell culture. Subsequent studies on adhesion, viability, differentiation, and proliferation of cultured myoblast cells, coupled with particle image velocimetry simulation, highlighted the potential of UV-irradiated LCE3 as a promising scaffold material for inducing surface morphology-induced cellular alignment and interactions.

Polyphenol-treatment without preceding glutaraldehyde fixation: a potential paradigm change for bioprosthetic heart valves

Abstract Background Glutaraldehyde (GA) is the common fixative agent for bioprosthetic heart valves (BHVs). However, its chemical instability can expose calcium binding sites and, at commercially used concentrations, GA does not ensure effective immunological tolerance, triggering an immune response correlated to degeneration. Recently, polyphenols (PPs) achieved an almost complete xenoantigens inactivation in GA-fixed BHVs ensuring chemical stability of the treated tissue while improving mechanical characteristics and adding anti-infective and anti-thrombotic properties [1-4]. Purpose A new PP-based treatment has been introduced as a potential GA substitute in BHV manufacturing. The unique chemical properties of PPs permit them to interact with the tissue through stable chemical bonds without depolymerization over time, achieving several improvements that promise to extend the long-term durability of BHVs (Fig.1). Methods The study compared the effects of two cross-linking methods on bovine pericardial tissue: (1) traditional fixation in GA, and (2) treatment with PPs without GA. The type of chemical interaction between PPs and tissue was evaluated through nuclear magnetic resonance. The xenoantigens inactivation was quantified in-vitro by ELISA test and in-vivo in a humanized mouse animal model. Biomechanical properties were assessed through uniaxial stress-strain tests and cross-link density through the shrinkage temperature test. The protective effect against bacterial adhesion was evaluated against a strain of S aureus, while the inhibition of thrombosis was evaluated in-vivo in a pig animal model and in-vitro in a blood-loop using bovine blood with radio-labeled platelets. Results PPs effectuated multiple chemical bonds with and within the pericardium including cross-links based on covalent and hydrogen bonds, stacking, and electrostatic interactions. The inactivation of over 90% of surface-xenoantigens of the treated tissue allowed for superior biocompatibility (compared to &amp;lt;50% by commercial GA concentrations). The increase in elongation exhibited by PP-treated tissue confirmed excellent biomechanical features (Fig.2) while a sufficient degree of cross-linking was demonstrated through an adequate shrinkage temperature. Furthermore, a significant degree of bacterial adhesion (86% inhibition evaluated with S. aureus) and thrombus formation (Fig.2, up to 90% inhibition) were observed. Conclusion There is a real clinical need for improved chemical stability, calcification resistance, and immunological tolerance of current BHVs (surgical and transcatheter). PP technology may substitute the use of GA extending their performance and durability, thereby opening trans-catheter heart valves to younger patients. Reducing the need for mechanical heart valves would also address the associated risks of lifelong anticoagulation therapy.Figure 1Figure 2

Distinct interactions with pentaalanine tuned by terminal structures of polyisoprene that determine their mechanical properties

The terminal aggregates of natural rubber exhibit multi-scale reinforcing effects, but the synthetic counterpart still lacks of readily available terminal functionalized polymers, and the corresponding terminal structure-function correlation remains obscure. In this work, by utilizing commercial raw materials, four kinds of polyisoprene (PIP) derivatives with different terminal structures (PEO, ene-PEO, COOH, H) were prepared and blended with pentaalanine to investigated the change of terminal structures and impact on rubber performance. It is revealed that the tight hydrogen-bonded β-sheet in the terminal nanoconfinements is correlated to the overall performance of the elastomers. As the polarity of the terminal group of the main chain increases, the content of the β-sheet formed with 5A also increases, and the corresponding properties such as tensile strength, dimensional stability, strain recovery, apparent activation energy and cross-linking density are all enhanced. Among them, two elastomers (PIP-PEO, PIP-ene-PEO) have high tensile strength and great dimensional stability, which are comparable to Malaysian natural rubber. These results present the multi-scale reinforcement process of terminal H-bonding aggregates due to the synergistic changes and stable co-assembly of polar main chains and peptide, giving an inspiration for the development of large-scale, high strength and creep resistant synthetic elastomers.