RESUMO
In this work, shape memory polymers (SMPs) were developed from a combination of a bio-based benzoxazine (BZ) monomer and polyurethane prepolymer (PU-prepolymer), both derived from bio-based raw materials. The bio-based BZ monomer (V-fa monomer) was synthesized through a Mannich condensation reaction using vanillin, paraformaldehyde, and furfurylamine. The bio-based PU-prepolymer was obtained by reacting palm oil polyol (MW = 1400 Da) and toluene diisocyanate (TDI). To investigate the curing behavior of poly(V-fa/urethane), with a mass ratio of 50/50, differential scanning calorimetry was employed. The structure of the resulting poly(V-fa/urethane) was confirmed using Fourier transform infrared spectroscopy. Furthermore, the synthesized V-fa/urethane copolymers with weight ratios of 70/30, 60/40, 50/50 and 40/60 were observed to exhibit shape memory behaviors induced by near-infrared irradiation (808 nm). Poly(V-fa/urethane), specifically with a mass ratio of 50/50, demonstrated superior shape memory performance. It exhibited a remarkable capacity to retain the temporary shape up to 90%, achieve 99% shape recovery, and exhibit a recovery time of 25 s. The shape memory properties were further improved with the addition of 3 wt% graphene nanoplatelets (GNPs), exhibiting an improvement in the shape fixity value to 94%, and shape recovery time value to 16 s. Moreover, our findings suggest that 60/40 poly(V-fa/urethane) reinforced with 3 wt% GNPs possesses favorable characteristics for applications as multiple SMPs, with shape fixity values of 97% and 94%, and shape recovery values of 96% and 89% for the first and second shapes, respectively.
RESUMO
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%.
RESUMO
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.
RESUMO
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.
