Comparative Effects of Hydrazine and Thermal Reduction Methods on Electromagnetic Interference Shielding Characteristics in Foamed Titanium Carbonitride MXene Films.

The urgent need for the development of micro-thin shields against electromagnetic interference (EMI) has sparked interest in MXene materials owing to their metallic electrical conductivity and ease of film processing. Meanwhile, postprocessing treatments can potentially exert profound impacts on their shielding effectiveness (SE). This work comprehensively compares two reduction methods, hydrazine versus thermal, to fabricate foamed titanium carbonitride (Ti3CNTx) MXene films for efficient EMI shielding. Upon treatment of ≈ 100 µm-thick MXene films, gaseous transformations of oxygen-containing surface groups induce highly porous structures (up to ≈ 74.0% porosity). The controlled application of hydrazine and heat allows precise regulation of the reduction processes, enabling tailored control over the morphology, thickness, chemistry, and electrical properties of the MXene films. Accordingly, the EMI SE values are theoretically and experimentally determined. The treated MXene films exhibit significantly enhanced SE values compared to the pristine MXene film (≈ 52.2 dB), with ≈ 38% and ≈ 83% maximum improvements for the hydrazine and heat-treated samples, respectively. Particularly, heat treatment is more effective in terms of this enhancement such that an SE of 118.4 dB is achieved at 14.3 GHz, unprecedented for synthetic materials. Overall, the findings of this work hold significant practical implications for advancing high-performance, non-metallic EMI shielding materials.

Multifunctional Applications Enabled by Fluorination of Hexagonal Boron Nitride.

2D materials exhibit exceptional properties as compared to their macroscopic counterparts, with promising applications in nearly every area of science and technology. To unlock further functionality, the chemical functionalization of 2D structures is a powerful technique that enables tunability and new properties within these materials. Here, the successful effort to chemically functionalize hexagonal boron nitride (hBN), a chemically inert 2D ceramic with weak interlayer forces, using a gas-phase fluorination process is exploited. The fluorine functionalization guides interlayer expansion and increased polar surface charges on the hBN sheets resulting in a number of vastly improved applications. Specifically, the F-hBN exhibits enhanced dispersibility and thermal conductivity at higher temperatures by more than 75% offering exceptional performance as a thermofluid additive. Dispersion of low volumes of F-hBN in lubricating oils also offers marked improvements in lubrication and wear resistance for steel tribological contacts decreasing friction by 31% and wear by 71%. Additionally, incorporating numerous negatively charged fluorine atoms on hBN induces a permanent dipole moment, demonstrating its applicability in microelectronic device applications. The findings suggest that anchoring chemical functionalities to hBN moieties improves a variety of properties for h-BN, making it suitable for numerous other applications such as fillers or reinforcement agents and developing high-performance composite structures.

Friction of Ti3C2Tx MXenes.

2D materials are well-known for their low-friction behavior by modifying the interfacial forces at atomic surfaces. Of the wide range of 2D materials, MXenes represent an emerging material class but their lubricating behavior has been scarcely investigated. Herein, the friction mechanisms of 2D Ti3C2Tx MXenes are demonstrated which are attributed to their surface terminations. We find that Ti3C2Tx MXenes do not exhibit the well-known frictional layer dependence of other 2D materials. Instead, the nanoscale lubricity of 2D MXenes is governed by the termination species resulting from synthesis. Annealing the MXenes demonstrate a 7% reduction in OH termination which translates to a 16-57% reduction of friction in agreement with DFT calculations. Finally, the stability of MXene flakes is demonstrated upon isolation from their aqueous environment. This work indicates that MXenes can provide sustainable lubricity at any thickness which makes them uniquely positioned among 2D material lubricants.

Electrochemically Responsive 3D Nanoarchitectures.

Responsive nanomaterials are being developed to create new unique functionalities such as switchable colors and adhesive properties or other programmable features in response to external stimuli. While many existing examples rely on changes in temperature, humidity, or pH, this study aims to explore an alternative approach relying on simple electric input signals. More specifically, 3D electrochromic architected microstructures are developed using carbon nanotube-Tin (Sn) composites that can be reconfigured by lithiating Sn with low power electric input (≈50 nanowatts). These microstructures have a continuous, regulated, and non-volatile actuation determined by the extent of the electrochemical lithiation process. In addition, this proposed fabrication process relies only on batch lithographic techniques, enabling the parallel production of thousands of 3D microstructures. Structures with a 30-97% change in open-end area upon actuation are demonstrated and the importance of geometric factors in the response and structural integrity of 3D architected microstructures during electrochemical actuation is highlighted.

Layered polymer composite foams for broadband ultra-low reflectance EMI shielding: a computationally guided fabrication approach.

The development of layered polymer composites and foams offers a promising solution for achieving effective electromagnetic interference (EMI) shielding while minimizing secondary electromagnetic pollution. However, the current fabrication process is largely based on trial and error, with limited focus on optimizing geometry and microstructure. This often results in suboptimal electromagnetic wave reflection and the use of unnecessarily thick samples. In this study, an input impedance model was employed to guide the fabrication of layered PVDF composite foams. This approach optimized the void fraction (VF) and the thickness of each layer to achieve broadband low reflection. Moreover, hybrid heterostructures of SiCnw@MXene were incorporated into the PVDF composite foams as an absorption layer, while the conductive PVDF/CNT composite foams served as a shielding layer. Directed by theoretical computations, we found that combining 2.2 mm of PVDF/SiCnw@MXene composite foam (50% VF) and 1.6 mm of PVDF/CNT composite yielded EMI shielding effectiveness of 45 dB, with an average reflectivity (R) of 0.03 and an effective absorption bandwidth of 5.54 GHz (for R < 0.1) over the Ku-band (12.4-18 GHz). Importantly, the corresponding peak R was only 0.000017. Our work showcases a theoretically guided approach for developing absorption-dominant EMI shielding materials with broadband ultra-low reflection, paving the way for cutting-edge applications.

Incorporating Loss Factor Modular Design for Full Ku-Band Microwave Attenuation in Double-Layered Graphene Aerogels.

The fabrication of absorption-dominant electromagnetic interference (EMI) shielding materials is a pressing priority to prevent secondary electromagnetic pollution in miniaturized electronic devices and communication systems. Meeting this goal has remained a tough challenge to keep pace with the rapid evolution of electronics due to the complex compositional and structural design and narrow operating bands. This work articulates a sound and simple strategy to precisely modulate the electrical conductivity of reduced graphene oxide (rGO), as the building block in lightweight double-layered rGO-film/rGO-aerogel/polyvinyl-alcohol (PVA) composites, for efficient microwave absorption over the entire Ku-band frequency range. These constructs reasonably comprised a porous absorption structure built from parallel rGO sheets aligned and prepared via freeze casting followed by freeze drying. The electrical conductivity and impedance of this layer were tuned by varying the annealing temperature from 400 to 800 °C, thereby adjusting the degree of reduction and the absorption characteristic. This layer was backed by a highly conductive rGO film reduced at a high temperature of 1000 °C, with a reflectivity of 97.5%. The incorporation of this film ensured high EMI shielding effectiveness of the double-layered structure through the absorption-reflection-reabsorption mechanism, consistent with the predicted values based on calculated loss factors and the input impedance of the structure. Accordingly, at an average EMI shielding effectiveness of 57.59 dB, the reflection shielding effectiveness (SER) and reflectivity (R) of the assembled composites were optimized to be as low as 0.22 dB and 0.049, respectively. This equates to approximately 99.999% shielding (SET) and ∼95% absorptivity (A) of the incident wave. This study opens new avenues for the development of lightweight (with a density as low as 15 mg/cm3) absorption-dominant EMI shielding composite materials with promising EMI shielding efficiency and potential applications in modern electronics.

Enhanced electrical properties of microcellular polymer nanocomposites via nanocarbon geometrical alteration: a comparison of graphene nanoribbons and their parent multiwalled carbon nanotubes.

Geometric factors of nanofillers considerably govern the properties of conductive polymer composites (CPCs). This study provides insights into how geometrical alteration through nanotube-to-nanoribbon conversion affects the electrical properties of solid and microcellular CPCs. In this regard, polyvinylidene fluoride (PVDF)-based nanocomposites are synthesized using both the parent multi-walled carbon nanotube (MWCNT) and its chemically unzipped product, i.e., graphene nanoribbons (GNRs). Theoretical and experimental results show that GNR-based composites exhibit 1-4 orders greater conductivities than MWCNT-based composites at the same filler loading because of the larger number of filler-filler junctions as well as the significantly greater contact areas. On the other hand, the conductivities of MWCNT-based and GNR-based composites are significantly increased by 230 times and 121 times, respectively, through microcellular foaming. The effective rearrangements of rigid MWCNTs and flexible GNRs (having 4 and 5 orders less bending stiffness) for network formation during cellular growth are compared. The GNR-based composites also exhibit a superior dielectric permittivity (e.g., 2.6 times larger real permittivity at a representative frequency of 103 Hz and a nanofiller loading of 4.2 vol%) compared to their MWCNT-based counterparts. This study demonstrates how the modification of the carbon fillers and the polymer matrix can dramatically enhance EMI shielding.

Greatly Enhanced Electromagnetic Interference Shielding Effectiveness and Mechanical Properties of Polyaniline-Grafted Ti3C2Tx MXene-PVDF Composites.

Nowadays, evolutions in wireless telecommunication industries, such as the emergence of complex 5G technology, occur together with massive development in portable electronics and wireless systems. This positive progress has come at the expense of significant electromagnetic interference (EMI) pollution, which requires the development of highly efficient shielding materials with low EM reflection. The manipulation of MXene surface functional groups and, subsequently, incorporation into engineered polymer matrices provide mechanisms to improve the electromechanical performance of conductive polymer composites (CPCs) and create a safe EM environment. Herein, Ti3C2Tx MXene nanoflakes were first synthesized and then, taking advantage of their abundant surface functional groups, polyaniline (PA) nanofibers were grafted onto the MXene surface via oxidant-free oxidative polymerization at two different MXene to monomer ratios. The electrical conductivity, EMI shielding effectiveness (SE), and mechanical properties of poly (vinylidene fluoride) (PVDF)-based CPCs at different nanomaterial loadings were then thoroughly investigated. A very low percolation threshold of 1.8 vol % and outstanding electrical conductivities of 0.23, 0.195, and 0.17 S/cm were obtained at 6.9 vol % loading for PVDF-MXene, PVDF-MX2AN1, and PVDF-MX1AN1, respectively. Compared to the pristine MXene composite, surface modification significantly enhanced the EMI SE of the PVDF-MX2AN1 and PVDF-MX1AN1 composites by 19.6 and 32.7%, respectively. The remarkable EMI SE enhancement of the modified nanoflakes was attributed to (i) the intercalation of PA nanofibers between MXene layers, resulting in better nanoflake exfoliation, (ii) a large amount of dipole and interfacial polarization dissipation by constructing capacitor-like structures between nanoflakes and polymer chains, and (iii) augmented EMI attenuation via conducting PA nanofibers. The surface modification of the MXene nanoflakes also enhanced the interfacial interactions between PVDF chains and nanoflakes, which resulted in an improved Young's modulus of the PVDF matrix by about 67 and 46% at 6.9 vol % loading for PVDF-MX2AN1 and PVDF-MX1AN1 composites, respectively.

Sectorization of Macromolecular Single Crystals Unveiled by Probing Shear Anisotropy.

Polymer single crystals continue to infiltrate emerging technologies such as flexible organic field-effect transistors because of their excellent translational symmetry and chemical purity. However, owing to the methodological challenges, direct imaging of the polymer chains folding direction resulting in sectorization of single crystals has rarely been investigated. Herein, we directly image the sectorization of polymer single crystals through anisotropic elastic deformation on the surface of macromolecular single crystals. A variant of friction force microscopy, in which the scanning direction of the probe tip is parallel with the cantilever axis, allows for high contrast imaging of the sectorization in polymer single crystals. The lateral deflection of the cantilever resulting from shear forces transverse to the scan direction shows a close connection with the in-plane components of the elastic tensor of the polymer single crystals, which is of a fundamentally different origin than the friction forces. This allows for fast, facile, and nondestructive characterization of the microstructure and in-plane elastic anisotropy of compliant crystalline materials such as polymers.

Layered Foam/Film Polymer Nanocomposites with Highly Efficient EMI Shielding Properties and Ultralow Reflection.

Lightweight, high-efficiency and low reflection electromagnetic interference (EMI) shielding polymer composites are greatly desired for addressing the challenge of ever-increasing electromagnetic pollution. Lightweight layered foam/film PVDF nanocomposites with efficient EMI shielding effectiveness and ultralow reflection power were fabricated by physical foaming. The unique layered foam/film structure was composed of PVDF/SiCnw/MXene (Ti3C2Tx) composite foam as absorption layer and highly conductive PVDF/MWCNT/GnPs composite film as a reflection layer. The foam layer with numerous heterogeneous interfaces developed between the SiC nanowires (SiCnw) and 2D MXene nanosheets imparted superior EM wave attenuation capability. Furthermore, the microcellular structure effectively tuned the impedance matching and prolonged the wave propagating path by internal scattering and multiple reflections. Meanwhile, the highly conductive PVDF/MWCNT/GnPs composite (~ 220 S m-1) exhibited superior reflectivity (R) of 0.95. The tailored structure in the layered foam/film PVDF nanocomposite exhibited an EMI SE of 32.6 dB and a low reflection bandwidth of 4 GHz (R < 0.1) over the Ku-band (12.4 - 18.0 GHz) at a thickness of 1.95 mm. A peak SER of 3.1 × 10-4 dB was obtained which corresponds to only 0.0022% reflection efficiency. In consequence, this study introduces a feasible approach to develop lightweight, high-efficiency EMI shielding materials with ultralow reflection for emerging applications.

Scalable Characterization of 2D Gallium-Intercalated Epitaxial Graphene.

Scalable synthesis of two-dimensional gallium (2D-Ga) covered by graphene layers was recently realized through confinement heteroepitaxy using silicon carbide substrates. However, the thickness, uniformity, and area coverage of the 2D-Ga heterostructures have not previously been studied with high-spatial resolution techniques. In this work, we resolve and measure the 2D-Ga heterostructure thicknesses using scanning electron microscopy (SEM). Utilizing multiple correlative methods, we find that SEM image contrast is directly related to the presence of uniform bilayer Ga at the interface and a variation of the number of graphene layers. We also investigate the origin of SEM contrast using both experimental measurements and theoretical calculations of the surface potentials. We find that a carbon buffer layer is detached due to the gallium intercalation, which increases the surface potential as an indication of the 2D-Ga presence. We then scale up the heterostructure characterization over a few-square millimeter area by segmenting SEM images, each acquired with nanometer-scale in-plane resolution. This work leverages the spectroscopic imaging capabilities of SEM that allows high-spatial resolution imaging for tracking intercalants, identifying relative surface potentials, determining the number of 2D layers, and further characterizing scalability and uniformity of low-dimensional materials.

Insight into the Directional Thermal Transport of Hexagonal Boron Nitride Composites.

Ideal dielectric materials for microelectronic devices should have high directionally tailored thermoconductivity with low dielectric constant and loss. Hexagonal boron nitride (hBN) with excellent thermal and dielectric properties shows a promise for the fabrication of thermoconductive dielectric polymer composites. Herein, a simple method for the fabrication of lightweight polymer/hBN composites with high directionally tailored thermoconductivity and excellent dielectric properties is presented. The solid polymer/hBN composites are manufactured by melt-compounding and injection molding. The porous composites are successfully manufactured in an injection molding process through supercritical fluid (SCF) foaming. X-ray tomography provides direct visualization of the internal microstructure and hBN orientation, leading to an in-depth understanding of the directionally dependent thermoconductivity of the polymer/hBN composite. Shear-induced orientation of hBN platelets in the solid HDPE/hBN composites leads to a significant anisotropic thermal conductivity. The solid HDPE/23.2 vol % hBN composites show an in-plane thermoconductivity as high as 10.1 W m-1 K-1, whereas the through-plane thermoconductivity is limited to 0.28 W m-1 K-1. However, the generation of a porous structure via SCF foaming imparts in situ exfoliation, random orientation, and interconnectivity of hBN platelets within the polymer matrix. This results in highly isotropic thermoconductivity with higher bulk thermal conductivity in the lightweight porous composites as compared to their solid counterparts. Furthermore, the electrically insulating composites developed in this study exhibit low dielectric constant and ultralow dielectric loss. Thus, this study presents a simple fabrication method to develop lightweight dielectric materials with tailored thermal conductivity for modern electronics.

Enhanced Electrical and Electromagnetic Interference Shielding Properties of Polymer-Graphene Nanoplatelet Composites Fabricated via Supercritical-Fluid Treatment and Physical Foaming.

Lightweight high-density polyethylene (HDPE)-graphene nanoplatelet (GnP) composite foams were fabricated via a supercritical-fluid (SCF) treatment and physical foaming in an injection-molding process. We demonstrated that the introduction of a microcellular structure can substantially increase the electrical conductivity and can decrease the percolation threshold of the polymer-GnP composites. The nanocomposite foams had a significantly higher electrical conductivity, a higher dielectric constant, a higher electromagnetic interference (EMI) shielding effectiveness (SE), and a lower percolation threshold compared to their regular injection-molded counterparts. The SCF treatment and foaming exfoliated the GnPs in situ during the fabrication process. This process also changed the GnP's flow-induced arrangement by reducing the melt viscosity and cellular growth. Moreover, the generation of a cellular structure rearranged the GnPs to be mainly perpendicular to the radial direction of the bubble growth. This enhanced the GnP's interconnectivity and produced a unique GnP arrangement around the cells. Therefore, the through-plane conductivity increased up to a maximum of 9 orders of magnitude and the percolation threshold decreased by up to 62%. The lightweight injection-molded nanocomposite foams of 9.8 vol % GnP exhibited a real permittivity of ε' = 106.4, which was superior to that of their regular injection-molded (ε' = 6.2). A maximum K-band EMI SE of 31.6 dB was achieved in HDPE-19 vol % GnP composite foams, which was 45% higher than that of the solid counterpart. In addition, the physical foaming reduced the density of the HDPE-GnP foams by up to 26%. Therefore, the fabricated polymer-GnP nanocomposite foams in this study pointed toward the further development of lightweight and conductive polymer-GnP composites with tailored properties.

Ultralight Microcellular Polymer-Graphene Nanoplatelet Foams with Enhanced Dielectric Performance.

Dielectric polymer nanocomposites with high dielectric constant (ε') and low dielectric loss (tan δ) are extremely desirable in the electronics industry. Percolative polymer-graphene nanoplatelet (GnP) composites have shown great promise as dielectric materials for high-performance capacitors. Herein, an industrially-viable technique for manufacturing a new class of ultralight polymer composite foams using commercial GnPs with excellent dielectric performance is presented. Using this method, the high-density polyethylene (HDPE)-GnPs composites with a microcellular structure were fabricated by melt-mixing. This was followed by supercritical fluid (SCF) treatment and physical foaming in an extrusion process, which added an extra layer of design flexibility. The SCF treatment effectively in situ exfoliated the GnPs in the polymer matrix. Moreover, the generation of a microcellular structure produced numerous parallel-plate nanocapacitors consisting of GnP pairs as electrodes with insulating polymer as nanodielectrics. This significantly increased the real permittivity and decreased the dielectric loss. The ultralight extruded HDPE-1.08 vol % GnP composite foams, with a 0.15 g·cm-3 density, had an excellent combination of dielectric properties (ε' = 77.5, tan δ = 0.003 at 1 × 105 Hz), which were superior to their compression-molded counterparts (ε' = 19.9, tan δ = 0.15 and density of = 1.2 g·cm-3) and to those reported in the literature. This dramatic improvement resulted from in situ GnP's exfoliation and dispersion, as well as a unique GnP parallel-plate arrangement around the cells. Thus, this facile method provides a scalable method to produce ultralight dielectric polymer nanocomposites, with a microscopically tailored microstructure for use in electronic devices.