Enhanced Mechanical Properties of 3D Printed Nanocomposites Composed of Functionalized Plant-Derived Biopolymers and Calcium-Deficient Hydroxyapatite Nanoparticles

Abstract

The combination of plant-derived polymer resins and mineral-based nanoparticles into three dimensional (3D) printable, high-performance nanocomposites suggests a means to improve the sustainability profile of rapid prototyping and additive manufacturing. In this work, our previously published nanocomposite biomaterial system of acrylated epoxidized soybean oil (AESO) and polyethylene glycol (PEGDA) diluent composited with calcium-deficient hydroxyapatite (nHA) nanorods was improved by the substitution of AESO with methacrylated AESO (mAESO) and the partial substitution of PEGDA with isosorbide methacrylate (IM). mAESO was used to increase the degree of crosslinking and reduce the ink viscosity. IM was synthesized by reacting the hydroxyl groups on isosorbide with methacrylic anhydride. The effects of partially replacing PEGDA with IM on the rheology and printability of the nanocomposite inks and the mechanical properties of the resulting nanocomposite materials were quantified. These masked stereolithography (mSLA) printed nanocomposites have greatly improved mechanical properties (tensile strength, Young’s modulus, and Mode-I fracture toughness) due to the shift to mAESO and IM. IM greatly improved the tensile fracture strength and Young’s modulus of the nanocomposites by acting as a reactive diluent and as a stiff segment in the polymer system. Dynamic mechanical analysis revealed that the glass transition temperature of the nanocomposite increased due to the addition of IM. However, IM decreased the strain-at–fracture, making the nanocomposites more brittle. This study demonstrates the development of high-performance mAESO-IM-nHA-based novel nanocomposites that can be easily 3D printed using desktop mSLA, suggesting a facile path forward to improved sustainability in rapid prototyping and additive manufacturing using nanocomposites for a broad range of applications.

Advanced Nanomaterials in Medical 3D Printing

“…[139] Adding these metal nanoparticles enables 3D-printed products to have excellent mechanical properties that match the mechanical properties required for bone tissue engineering. Some inorganic non-metallic nanoparticles are also used to improve the mechanical properties of materials, such as ceramic nanoparticles, [140] hydroxyapatite nanoparticles, [141] and silica nanoparticles, [142] which not only have ideal mechanical properties in bone tissue repair, but also can be used as a source of calcium required for bone repair to promote bone tissue repair. The above enhancement of the mechanical properties of 3D printing products is mainly based on the strong mechanical properties of the nanoparticles themselves to enhance other components to improve the mechanical properties of the original material system.…”

In Vivo Osteogenic and Angiogenic Properties of a 3D-Printed Isosorbide-Based Gyroid Scaffold Manufactured via Digital Light Processing

“…CSMA-2 is an isosorbide-based polymer derived from sustainable sources such as starch and cellulose. Sustainable plant-derived photopolymers offer environmentally friendly materials to substitute fuel-based commercial photopolymers [ 3 ]. Isosorbide has desirable stiffness for hard tissue engineering due to its ring structure.…”

“…In addition, the good optical transparency of isosorbide is also advantageous for its development as a 3D printing material, especially for lithography methods. Isosorbide can serve as the backbone for polymers with methacrylate or acrylate groups as the functional groups [ 3 ]. Several studies have demonstrated successful 3D printing with various isosorbide-based composites for hard tissue engineering [ 3 , 4 , 5 ].…”

“…Isosorbide can serve as the backbone for polymers with methacrylate or acrylate groups as the functional groups [ 3 ]. Several studies have demonstrated successful 3D printing with various isosorbide-based composites for hard tissue engineering [ 3 , 4 , 5 ].…”

Improving the 3D Printability and Mechanical Performance of Biorenewable Soybean Oil-Based Photocurable Resins

“…Although AESO can be UV cured without any other comonomers [15,16], the addition of small amounts of a crosslinking agent, such as polyethylene glycol diacrylate or polycaprolactone diacrylate, has shown to facilitate its photopolymerization and control the final properties of the polymer networks, such as tensile strength and elongation at the break [17]. For DLP or SLA applications, usually (meth)acrylates with functionality up to three are employed, such as hydroxyethyl methacrylate (HEMA) [22], isobornyl methacrylate (IBOMA) [12,23], isobornylacrylate (IBOA) [24], tetrahydrofurfuryl methacrylate (THFMA) [12], 1,6-hexanediol diacrylate (HDDA), [10,25] polyethylene diacrylate (PEGDA) [26][27][28], trimethylolpropane triacrylate (TMPTA) [10,25] or other compounds such as acryloylmorpholine (ACMO) [10]. A summary of these references has been included, although comparisons between them are difficult due to the different experimental conditions and products used, including the origin of the soybean acrylate oil, either commercial or specifically synthesized for the study.…”