Crosslinking Techniques in Polymeric Materials
Summary
Crosslinking transforms linear or branched polymer chains into three-dimensional networks by forming covalent or ionic bonds between chains. This network formation sharply elevates mechanical strength, thermal resistance and chemical stability, while often reducing melt flow and crystallinity. Conventional chemical crosslinking typically employs peroxides, silanes or multifunctional monomers. Peroxide crosslinking proceeds via free-radical initiation, generating carbon-centred radicals that abstract hydrogen atoms and recombine to form C–C crosslinks. Silane grafting introduces alkoxysilane moieties onto polyolefin backbones, followed by moisture-induced hydrolysis and condensation to yield Si–O–Si bridges. Radiation (electron beam or gamma rays) offers a catalyst-free route, where high-energy photons induce direct chain scission and recombination. Emerging strategies include dynamic covalent crosslinks—such as disulfide or boronic esters—that endow networks with reprocessability and self-healing, and photo-mediated systems that allow spatial and temporal control over crosslink density. Tuning crosslink density and network architecture enables the design of elastomers, thermosets and thermoplastic elastomers for applications ranging from soft robotics and biomedical implants to high-performance composites and sustainable packaging.
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Crosslinking Techniques in Polymeric Materials publication trend
The graph below shows the total number of articles in crosslinking techniques in polymeric materials across all publications each year (not limited to Nature Index journals).
Technical terms
Crosslink density: Number of crosslinks per unit volume, determining network stiffness and thermal resistance.
Gel content: Fraction of insoluble polymer network after solvent extraction, indicating crosslinked fraction.
Free-radical initiator: Compound (e.g., peroxide) that thermally decomposes to generate radicals, triggering crosslink formation.
Long-chain branching: Formation of polymer side-chains via crosslinking, enhancing entanglement and mechanical strength.
Reactive extrusion: Continuous processing method combining melt mixing with in situ chemical reactions (e.g., grafting or crosslinking).
References
- A versatile modification strategy to enhance polyethylene properties through solution-state peroxide modifications. Polymer Chemistry (2024).
- The effect of chemical crosslinking on the properties of Rotomolded high density polyethylene. Journal of Applied Polymer Science (2023).
- The Effect of Dialkyl Peroxide Crosslinking on the Properties of LLDPE and UHMWPE. Polymers (2021).
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