Abstract
The use of renewable sources for optical 3D printing instead of petroleum-based materials is increasingly growing. Combinations of photo- and thermal polymerization in dual curing processes can enhance the thermal and mechanical properties of the synthesized thermosets. Consequently, thiol-ene/thiol-epoxy polymers were obtained by combining UV and thermal curing of acrylated epoxidized soybean oil and epoxidized linseed oil with thiols, benzene-1,3-dithiol and pentaerythritol tetra(3-mercaptopropionate). Thiol-epoxy reaction was studied by calorimetry. The changes of rheological properties were examined during UV, thermal and dual curing to select the most suitable formulations for laser direct writing (LDW). The obtained polymers were characterized by dynamic-mechanical thermal analysis, thermogravimetry, and mechanical testing. The selected dual curable mixture was tested in LDW 3D lithography for validating its potential in optical micro- and nano-additive manufacturing. The obtained results demonstrated the suitability of epoxidized linseed oil as a biobased alternative to bisphenol A diglycidyl ether in thiol-epoxy thermal curing reactions. Dual cured thermosets showed higher rigidity, tensile strength, and Young’s modulus values compared with UV-cured thiol-ene polymers and the highest thermal stability from all prepared polymers. LDW results proved their suitability for high resolution 3D printing—individual features reaching an unprecedented 100 nm for plant-based materials. Finally, the biobased resin was tested for thermal post-treatment and 50% feature downscaling was achieved.
Highlights
Laser direct writing (LDW) is a progressive 3D printing technology, which enables production of three-dimensional micro- and nanostructures with variable architectures [1].laser direct writing (LDW) is widely applied in polymer additive manufacturing due to its flexibility [2] and precise spatial and lateral resolution [3]
The dual curing process could be adapted for optical 3D printing (O3DP) technologies
Thermal post curing of acrylate resins was tested in LDW, which was found to facilitate the high property reproducibility that is essential for any application [8]
Summary
Laser direct writing (LDW) is a progressive 3D printing technology, which enables production of three-dimensional micro- and nanostructures with variable architectures [1].LDW is widely applied in polymer additive manufacturing due to its flexibility [2] and precise spatial and lateral resolution [3]. In polymer additive manufacturing, (meth)acrylate and epoxy monomers has been widely used for optical 3D printing (O3DP) [5]. A promising way to enhance the thermal-mechanical properties of polymers is to combine similar or different stimuli such as temperature or UV light in dual curing process [6,7]. Dual curing stereolithographic resins from petroleum-based acrylate and epoxy monomers were formulated and presented as suitable for producing materials with different shape and size [9,10,11]. This area is still largely unexplored as limited amount of publications have been published so far [12]
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