The effects of ethanol on the physicochemical, structural and in vitro digestive properties of Tartary buckwheat starch-quercetin/rutin complexes (e-TBSQ and e-TBSR) were investigated. Ethanol restricted the gelatinization of Tartary buckwheat starch (TBS), which resulted an increase in ∆H, G' and G" as well as a decrease in apparent viscosity of e-TBSQ and e-TBSR. The particle size, scanning electron microscopy and X-ray diffraction results showed that ethanol influenced the morphological structure of TBS granules and the starch crystalline structure in e-TBSQ and e-TBSR changed from B-type to V-type when the ethanol concentration was 25%. Saturation transfer difference-nuclear magnetic resonance results revealed that ethanol weakened the binding ability of quercetin/rutin to TBS in e-TBSQ and e-TBSR, leading to a change in the binding site on the quercetin structural unit. The residual ungelatinized TBS granules in e-TBSQ and e-TBSR induced a high slowly digestible starch content, and thus displayed a "resistant-to-digestion".
Digestion , Ethanol , Fagopyrum , Quercetin , Rutin , Starch , Fagopyrum/chemistry , Starch/chemistry , Quercetin/chemistry , Ethanol/chemistry , Viscosity , Rutin/chemistry , Particle Size , Plant Extracts/chemistry , Models, Biological , X-Ray Diffraction
Extrusion-based three-dimensional (3D) printing techniques usually exhibit anisotropic thermal, mechanical, and electric properties due to the shearing-induced alignment during extrusion. However, the transformation from the extrusion to stacking process is always neglected and its influence on the final properties remains ambiguous. In this work, we adopt two different sized boron nitride (BN) sheets, namely, small-sized BN (S-BN) and large-sized BN (L-BN), to explore their impact on the orientation degree, morphology, and final anisotropic thermal conductivity (TC) of thermoplastic polyurethane (TPU) composites by fused deposition modeling. The transformation from one-dimensional axial alignment in the extruded filament to two-dimensional alignment (horizontal and vertical alignment) in the stacking filament of BN sheets is observed, and its impact on anisotropic TC in three directions is clarified. It is found that L-BN/TPU composites show a high TC of 6.45 W m-1 K-1 at 60 wt % BN content along the printing direction, while at a lower content (<40 wt %), S-BN/TPU composites exhibit a higher TC than L-BN/TPU composites. Effects of orientation, viscosity, and voids are comprehensively considered to elucidate such differences. Finally, heat dissipation tests demonstrate the great potential of 3D printed BN/TPU composites to be used in thermal management applications.
Efficient thermal transportation in a preferred direction is highly favorable for thermal management issues. The combination of 3D printing and two-dimensional (2D) materials such as graphene, BN, and so on enables infinite possibilities for hierarchically aligned structure programming. In this work, we report the formation of the asymmetrically aligned structure of graphene filled thermoplastic polyurethane (TPU) composites during 3D printing process. The as-printed vertically aligned structure demonstrates a through-plane thermal conductivity (TC) up to 12 W m-1 K-1 at 45 wt % graphene content, which is â¼8 times of that of a horizontally printed structure and surpasses many of the traditional particle reinforced polymer composites. The superior TC is mainly attributed to the anisotropic structure design that benefited from the preferable degree of orientation of graphene and the multiscale dense structure realized by finely controlling the printing parameters. Finite element method (FEM) confirms the essential impact of anisotropic TC design for highly thermal conductive composites. This study provides an effective way to develop 3D printed graphene-based polymer composites for scalable thermal-related applications such as battery thermal management, electric packaging, and so on.
The rapid progress in silicon carbide (SiC)-based technology for high-power applications expects an increasing operation temperature (up to 250 °C) and awaits reliable packaging materials to unleash their full power. Epoxy-based encapsulant materials failed to provide satisfactory protection under such high temperatures due to the intrinsic weakness of epoxy resins, despite their unmatched good adhesion and processability. Herein, we report a series of copolymers made by melt blending novolac cyanate ester and tetramethylbiphenyl epoxy (NCE/EP) that have demonstrated much superior high-temperature stability over current epoxies. Benefited from the aromatic, rigid backbone and the highly functional nature of the monomers, the highest values achieved for the copolymers are as follows: glass-transition temperature (Tg) above 300 °C, decomposition onset above 400 °C, and char yield above 45% at 800 °C, which are among the highest of the known epoxy chemistry by far. Moreover, the high-temperature aging (250 °C) experiments showed much reduced mass loss of these copolymers compared to the traditional high-temperature epoxy and even the pure NCE in the long term by suppressing hydrolysis degradation mechanisms. The copolymer composition, i.e., NCE to EP ratio, has found to have profound impacts on the resin flowability, thermomechanical properties, moisture absorption, and dielectric properties, which are discussed in this paper with in-depth analysis on their structure-property relationships. The outstanding high-temperature stability, preferred and adjustable processability, and the dielectric properties of the reported NCE/EP copolymers will greatly stimulate further research to formulating robust epoxy molding compounds (EMCs) or underfill for packaging next-generation high-power electronics.
Thermally conductive composites have attracted great attention in virtue of their crucial role in thermal management. In this work, laminated composites were prepared by laying graphite films (GF) and carbon fiber fabrics (CF) in a certain order, then penetrating thermoplastic polyurethane (TPU), finally hot-pressing. In order to enhance the inter-layer strength, the graphite films were perforated with arrays of 1 mm holes in diameter which have intervals of 4 mm and permit the seeping of liquid TPU through them. The in-plane thermal conductivity (TC) of composite reaches 242 W m-1 K-1 with the loading of 25 vol% GF and 60 vol% CF, which is 1210 times that of pure TPU. The great improvement of TC is ascribed to the thermal conductive pathways formed by continuous GF with ultrahigh TC. The addition of CF enhances markedly the mechanical properties of composites. Bending strength and modulus of composites are 5.56 and 17.09 times that of pure TPU, respectively. The proposed design and manufacture method are facile and effective to obtain polymeric composites simultaneously with high TC and good mechanical properties.
To meet the increasing demands for effective heat management of electronic devices, a graphene-based polymeric composite is considered to be one of the candidate materials owing to the ultrahigh thermal conductivity (TC) of graphene. However, poor graphene dispersion, low quality of exfoliated graphene, and strong phonon scattering at the graphene/matrix interface restrict the heat dissipation ability of graphene-filled composites. Here, a facile and versatile approach to bond graphene foam (GF) with polydimethylsiloxane (PDMS) is proposed, and the corresponding composite with considerable improvement in TC and insulativity is fabricated. First, three-dimensional GF was coated with polydopamine (PDA) via π-π stack and functional groups from PDA reacted with 3-aminopropyltriethoxysilane (APTS). Then, the modified GF was compressed (c-GF) to enhance density and infiltrated with PDMS to get the c-GF/PDA/APTS/PDMS composite. As a result, these processes endow the composite with high TC of in-plane 28.77 W m-1 K-1 and out-of-plane 1.62 W m-1 K-1 at 11.62 wt % GF loading. Besides, the composite manifests obvious improvement in mechanical properties, thermal stability, and insulativity compared to neat PDMS and GF/PDMS composite. An attempt to use the composite for cooling a ceramic heater is found to be successful. Above results open a way for such composites to be applied for the heat management of electronic devices.
