Smart materials with light-actuated shape memory effects are developed from renewable resources in this work. Bio-based benzoxazine resin is prepared from vanillin, furfurylamine, and paraformaldehyde by utilizing the Mannich-like condensation. Vanillin-furfurylamine-containing benzoxazine resin (V-fa) is subsequently copolymerized with epoxidized castor oil (ECO). When the copolymer is reinforced with multiwalled carbon nanotubes (MWCNTs), the resulting composite exhibits shape memory effects. Molecular characteristics of V-fa resin, ECO, and V-fa/ECO copolymers are obtained from Fourier transform infrared (FT-IR) spectroscopy. Curing behavior of V-fa/ECO copolymers is investigated by differential scanning calorimetry. Dynamic mechanical properties of MWCNT reinforced V-fa/ECO composites are determined by dynamic mechanical analysis. Morphological details and distribution of MWCNTs within the copolymer matrix are characterized by transmission electron microscopy. Shape memory performances of MWCNT reinforced V-fa/ECO composites are studied by shape memory tests performed with a universal testing machine. After a significant deformation to a temporary shape, the composites can be recovered to the original shape by near-infrared (NIR) laser actuation. The shape recovery process can be stimulated at a specific site of the composite simply by focusing NIR laser to that site. The shape recovery time of the composites under NIR actuation is four times faster than the shape recovery process under conventional thermal activation. Furthermore, the composites possess good shape fixity and good shape recovery under NIR actuation.

A series of substituted polybenzoxazines was synthesized and studied as binders in non-asbestos friction composite materials. The structures of the polybenzoxazines were varied in a systemic fashion by increasing the number and position of pendant alkyl (methyl) groups and was accomplished using the respective aromatic amines during the polymer synthesis step. By investigating the key thermomechanical and tribological characteristics displayed by the composite materials, the underlying structure-properties relationships were deconvoluted. Composite friction materials with higher thermomechanical and wear resistance properties were obtained from polybenzoxazines with relatively high crosslink densities. In contrast, polybenzoxazines with relatively low crosslink densities afforded composite friction materials with an improved coefficient of friction values and specific wear rates.

In this research, benzoxazine (BA-a) and diamino polysiloxane (PSX750) blends were prepared at 0–50 wt% of BA-a. The interactions between two polymeric components were investigated via a Fourier Transform Infrared Spectrometer (FT-IR). The thermal properties of the blends were also determined with Dynamic Mechanical Analyzer (DMA) and Thermogravimetric Analyzer (TGA). The mechanical properties and shape memory behaviors of the blends were also investigated. The FTIR spectra exhibited the shift of the peak from 1672 to the range of 1634–1637 cm⁻¹, which could be identified as hydrogen bonds between two polymeric domains at the contents from 30 to 50 wt%. The DMA thermograms revealed two glass transition temperatures, which could indicate a partially miscible system. The char yield values were increased, while the decomposition temperatures were decreased with an increasing benzoxazine content. Interestingly, the blends at the contents of 10 and 20 wt% presented dual-shape memory behaviors, whereas triple- or multiple-shape memory behaviors were observed with benzoxazine contents of 30 to 50 wt%. For the high-temperature recovery state, a shape memory ratio of 97.5% with a recovery time of 65 s and a shape fixity ratio of 66.7% was recorded at the content of 50 wt%. For the low-temperature recovery state, a shape recovery ratio of 98.9% was observed at the same content. Moreover, the values of the recovery ratio for four shape-recovery cycles revealed multiple shape memory behaviors with high recovery ratios in the range of 95–98%.

In this research, blends of bio-based polybenzoxazine (V-fa) and polycaprolactone (PCL) with different molecular weights (M_n) (14,000, 45,000, and 80,000 Da) were prepared with varying PCL content from 10 to 95 wt%. The spectra measured using Fourier Transform Infrared Spectroscopy (FTIR) may indicate the presence of hydrogen bonding between two polymeric components. The thermograms obtained using a Differential Scanning Calorimeter (DSC) and dynamic mechanical analyzer (DMA) exhibited a shift in glass transition temperature (T_g), which indicated partial miscibility between V-fa and PCL. The thermograms obtained using a thermogravimetric analyzer (TGA) revealed that the addition of PCL led to an increase in the maximum decomposition temperature (T_dmax). The tensile strength and modulus decreased with an increase in PCL, thus indicating a decrease in brittleness. Interestingly, only the samples with an M_n of 80,000 Da were bendable. The blends with 80 wt% PCL were revealed to have shape memory behaviors with a shape fixity of approximately 81%. The shape recovery ratio of the blends with 95 wt% PCL was approximately 78%.

In this study, the blends of bio-based polybenzoxazine (V-fa type) and poly(ethylene glycol) (PEG) with PEG contents from 50 to 95 wt% and different molecular weights were developed to improve the flexibility of thermosetting polymers. Of these blends, PEG 8k at 80 wt%, which exhibited the best processability, was selected for further development via compositing with carbon black (CB) from 0 to 20 phr. Differential Scanning Calorimetry (DSC) analysis revealed that the melting temperature (T_m) increased from 70 to 83 °C and glass transition temperatures (T_g) increased from –53 to –48 °C at 20 phr. Thermogravimetric Analysis (TGA) demonstrated high thermal stability, with T_dmax (for all CB contents) presented at ca. 416 °C. Moreover, char yield was increased from 10% (without CB) to 28% (20 phr), reflecting improved decomposition resistance. Mechanical properties demonstrated that CB significantly reinforced the composites. The flexural modulus and flexural strength were increased from 117.18 MPa (without CB) to 456 MPa (10 phr) and from 2.42 MPa (without CB) to 3.94 MPa (2.5 phr), respectively. The SEM images confirmed uniform morphology and good filler dispersion. Conclusively, the composites of 8k PEG 80 wt% filled with 2.5 phr of CB provided an optimal balance of mechanical and thermal stability and engineering polymer applications.