Enhancing the Matrix-Fiber Interface with a Surfactant Leads to Improved Performance Properties of 3D Printed Composite Materials Containing Cellulose Nanofibrils.

Cellulose nanofibrils (CNFs) exhibit characteristics that make them a desirable addition to new composite materials. CNFs are usable in a wide variety of applications such as coatings, personal and healthcare products, packaging, and advanced structural materials. They can also help overcome some performance issues with objects 3D printed by stereolithography (SLA) including dimensional instability and poor mechanical properties. However, CNFs are hydrophilic, making their dispersion in hydrophobic resins common to SLA difficult. Therefore, improvement of performance properties will not be fully realized. In this work, we treated TEMPO-oxidized CNFs (TOCNFs) with the hydrochloride salt of lauroyl arginate ethyl ester (LAE·HCl), a cationic surfactant, to investigate how this coating would affect the performance properties of multicomponent uncured SLA resins and subsequently printed objects. We hypothesized this coating would enhance the dispersion of the cellulose nanomaterials when compared to their uncoated counterparts, which would lead to quantifiable differences among the sample groups. We found that the viscosity of a commercial 3D printing resin (0.34 Pa·s at 30 Hz) increased by nearly an order of magnitude upon addition of even 1 wt % uncoated TOCNFs (2.96 Pa·s at 30 Hz). Moreover, the tensile strength (19.9(5) MPa) and modulus (0.65(5) GPa) of objects printed from the commercial resin decreased when adding 4 wt % uncoated TOCNF (12.5(2) MPa and 0.58(8) GPa, respectively). In contrast, resins having 4 wt % TOCNFs coated with LAE were less viscous (1.25 Pa·s at 30 Hz), and objects printed from them had enhanced tensile strength (24.7(7) MPa) and modulus (0.78(8) GPa) when compared to both the unadulterated resin and that having uncoated TOCNFs. Our findings show the general utility of using a surfactant with cellulose nanomaterials to homogenize multicomponent resins for 3D printing composite materials with enhanced performance properties.

Structural Insight in the Interfacial Effect in Ferroelectric Polymer Nanocomposites.

Both experimental results and theoretical models suggest the decisive role of the filler-matrix interfaces on the dielectric, piezoelectric, pyroelectric, and electrocaloric properties of ferroelectric polymer nanocomposites. However, there remains a lack of direct structural evidence to support the so-called interfacial effect in dielectric nanocomposites. Here, a chemical mapping of the interfacial coupling between the nanofiller and the polymer matrix in ferroelectric polymer nanocomposites by combining atomic force microscopy-infrared spectroscopy (AFM-IR) with first-principles calculations and phase-field simulations is provided. The addition of ceramic fillers into a ferroelectric polymer leads to augmentation of the local conformational disorder in the vicinity of the interface, resulting in the local stabilization of the all-trans conformation (i.e., the polar ß phase). The formation of highly polar and inhomogeneous interfacial regions, which is further enhanced with a decrease of the filler size, has been identified experimentally and verified by phase-field simulations and density functional theory (DFT) calculations. This work offers unprecedented structural insights into the configurational disorder-induced interfacial effect and will enable rational design and molecular engineering of the filler-matrix interfaces of electroactive polymer nanocomposites to boost their collective properties.

Tunable Ferromagnetism and Thermally Induced Spin Flip in Vanadium-Doped Tungsten Diselenide Monolayers at Room Temperature.

The outstanding optoelectronic and valleytronic properties of transition metal dichalcogenides (TMDs) have triggered intense research efforts by the scientific community. An alternative to induce long-range ferromagnetism (FM) in TMDs is by introducing magnetic dopants to form a dilute magnetic semiconductor. Enhancing ferromagnetism in these semiconductors not only represents a key step toward modern TMD-based spintronics, but also enables exploration of new and exciting dimensionality-driven magnetic phenomena. To this end, tunable ferromagnetism at room temperature and a thermally induced spin flip (TISF) in monolayers of V-doped WSe2 are shown. As vanadium concentration increases, the saturation magnetization increases, which is optimal at ≈4 at% vanadium; the highest doping level ever achieved for V-doped WSe2 monolayers. The TISF occurs at ≈175 K and becomes more pronounced upon increasing the temperature toward room temperature. The TISF can be manipulated by changing the vanadium concentration. The TISF is attributed to the magnetic-field- and temperature-dependent flipping of the nearest W-site magnetic moments that are antiferromagnetically coupled to the V magnetic moments in the ground state. This is fully supported by a recent spin-polarized density functional theory study. The findings pave the way for the development of novel spintronic and valleytronic nanodevices and stimulate further research.

Deconvoluting the Photonic and Electronic Response of 2D Materials: The Case of MoS2.

Evaluating and tuning the properties of two-dimensional (2D) materials is a major focus of advancing 2D science and technology. While many claim that the photonic properties of a 2D layer provide evidence that the material is "high quality", this may not be true for electronic performance. In this work, we deconvolute the photonic and electronic response of synthetic monolayer molybdenum disulfide. We demonstrate that enhanced photoluminescence can be robustly engineered via the proper choice of substrate, where growth of MoS2 on r-plane sapphire can yield >100x enhancement in PL and carrier lifetime due to increased molybdenum-oxygen bonding compared to that of traditionally grown MoS2 on c-plane sapphire. These dramatic enhancements in optical properties are similar to those of super-acid treated MoS2, and suggest that the electronic properties of the MoS2 are also superior. However, a direct comparison of the charge transport properties indicates that the enhanced PL due to increased Mo-O bonding leads to p-type compensation doping, and is accompanied by a 2x degradation in transport properties compared to MoS2 grown on c-plane sapphire. This work provides a foundation for understanding the link between photonic and electronic performance of 2D semiconducting layers, and demonstrates that they are not always correlated.