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1. Thermoresponsive, Recyclable, Conductive, and Healable Polymer Nanocomposites with Three Distinct Dynamic Bonds

   https://doi.org/10.1021/acsapm.2c00790  

   Dodo, Obed J. ; Petit, Leilah ; Dunn, Derrick ; Myers, Camryn P. ; Konkolewicz, Dominik ( September 2022 , ACS Applied Polymer Materials)

   Integration of multiple types of dynamic linkages into one polymer network is challenging and not well understood especially in the design and fabrication of dynamic polymer nanocomposites (DPNs). In this contribution, we present facile methods for synthesizing flexible, healable, conductive, and recyclable thermoresponsive DPNs using three dynamic chemistries playing distinct roles. Dynamic hydrogen bonds account for material flexibility and recycling character. Thiol-Michael exchange accounts for thermoresponsive properties. Diels–Alder reaction leads to covalent bonding between polymer matrix and nanocomposite. Overall, the presence of multiple types of orthogonal dynamic bonds provided a solution to the trade-off between enhanced mechanical performance and material elongation in DPNs. Efficient reinforcement was achieved using <1 wt % multiwalled carbon nanotubes as nanocomposite. Resulting DPNs showed excellent healability with over 3 MPa increase in stress compared to unreinforced materials. Due to multiple responsive dynamic linkages, >90% stress–relaxation was observed with self-healing achieved within 1 h of healing time. Increased mechanical strength, electrical conductivity, and reprocessability were achieved all while maintaining material flexibility and extensibility, hence highlighting the strong promise of these DPNs in the rapidly growing fields of flexible compliant electrodes and strain sensors. 

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2. Development of Nanocomposite Thermoelectric Generators for Body Heat Harvesting

   Chloe Flack, Baiyu Zhang ( January 2019 , Undergraduate Research Symposium)

   This work evaluates wearable thermoelectric (TE) devices consisting of nanocomposite thermoelectric materials, aluminum nitride ceramic headers, and a flexible and stretchable circuit board. These types of wearable systems are part of a broader effort to harvest thermal energy from the body and convert it into electrical energy to power wearable electronics. Thermoelectric generators are made of p-type (Bi,Sb)2Te3 and n-type Bi2(Te,Se)3. The nanocomposite thermoelectric materials investigated in this research address the two fundamental challenges for body heat harvesting. The first challenge is related to the unavailability of high zT n-type materials near the body temperature. The second challenge is related to the thermoelectric power factor. To improve the zT, one has to increase the power factor simultaneously while reducing the thermal conductivity. Our nanocomposites result in enhancement of the TE power factor along with the reduction of the thermal conductivity. The fundamental reason is a nanoscale effect that happens only when the energy distribution function of the carriers does not relax to that of the bulk material in the crystallites. Ten p-type and ten n-type nanocomposite ingots were synthesized and characterized in this research. All ingots were characterized versus their thermoelectric properties and they all showed similarly enhanced properties. Our nanocomposites, compared to commercial materials, have better zT and thermal resistivity by 40% and 75% for p-type, respectively, and 15% and 140% for n-type. Compared to the state-of-the-art materials, our nanocomposites produce significantly higher power due to their optimized properties for the body temperature. 

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3. Data centric nanocomposites design via mixed-variable Bayesian optimization

   https://doi.org/10.1039/d0me00079e  

   Iyer, Akshay ; Zhang, Yichi ; Prasad, Aditya ; Gupta, Praveen ; Tao, Siyu ; Wang, Yixing ; Prabhune, Prajakta ; Schadler, Linda S. ; Brinson, L. Catherine ; Chen, Wei ( January 2020 , Molecular Systems Design & Engineering)

   With an unprecedented combination of mechanical and electrical properties, polymer nanocomposites have the potential to be widely used across multiple industries. Tailoring nanocomposites to meet application specific requirements remains a challenging task, owing to the vast, mixed-variable design space that includes composition ( i.e. choice of polymer, nanoparticle, and surface modification) and microstructures ( i.e. dispersion and geometric arrangement of particles) of the nanocomposite material. Modeling properties of the interphase, the region surrounding a nanoparticle, introduces additional complexity to the design process and requires computationally expensive simulations. As a result, previous attempts at designing polymer nanocomposites have focused on finding the optimal microstructure for only a fixed combination of constituents. In this article, we propose a data centric design framework to concurrently identify optimal composition and microstructure using mixed-variable Bayesian optimization. This framework integrates experimental data with state-of-the-art techniques in interphase modeling, microstructure characterization and reconstructions and machine learning. Latent variable Gaussian processes (LVGPs) quantifies the lack-of-data uncertainty over the mixed-variable design space that consists of qualitative and quantitative material design variables. The design of electrically insulating nanocomposites is cast as a multicriteria optimization problem with the goal of maximizing dielectric breakdown strength while minimizing dielectric permittivity and dielectric loss. Within tens of simulations, our method identifies a diverse set of designs on the Pareto frontier indicating the tradeoff between dielectric properties. These findings project data centric design, effectively integrating experimental data with simulations for Bayesian Optimization, as an effective approach for design of engineered material systems. 

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4. 0‐3 magnetic nanocomposites via EPD: Current status for power component fabrication and future directions

   https://doi.org/10.1111/jace.19412  

   Mills, Sara C. ; Patterson, Eric A. ; Andrew, Jennifer S. ( August 2023 , Journal of the American Ceramic Society)

   Inductors and transformers (here referred to as power components) for modern AC/DC switching power supplies require magnetic materials that have high power density and efficiency at high frequencies, with high magnetic saturation, low coercivity, and multi‐micrometer thicknesses to increase magnetic energy storage and power handling. Rather than using a single‐phase magnetic material in a polymer‐based composite, a composite formed from two magnetic phases (such as a 0‐3 nanocomposite) can simultaneously achieve all of the listed requirements and benefit from contributions by both the zero‐ and three‐dimensional phases to the magnetic properties. The fabrication of 0‐3 magnetic nanocomposites for power component applications requires a method to deposit magnetic nanoparticles into thick, physically stable yet porous films, and a subsequent method for infiltrating the magnetic nanoparticle film with another magnetic material. Here, the deposition of magnetic nanoparticles into micron‐thick films using electrophoretic deposition (EPD) is discussed. This is described along with a new method, to improve upon traditional EPD methods by increasing film–substrate interactions with chelating agents, therefore increasing film stability. Next, the use of electro‐infiltration for fully incorporating a secondary magnetic material within the nanoparticle film is presented, showing the cumulative fabrication process with the addition of a multilayered nanocomposite fabrication technique for increasing overall nanocomposite thickness. The subsequent cross‐sectional and magnetic characterization of the fabricated 0‐3 nanocomposites is also shown. Finally, future directions for 0‐3 magnetic nanocomposites are offered, with emphasis on potential materials synthesis techniques and on translating knowledge beyond power component applications.

    

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5. Recent Advances in the Synthesis of Polymer-Grafted Low-K and High-K Nanoparticles for Dielectric and Electronic Applications

   https://doi.org/10.3390/molecules26102942  

   Tawade, Bhausaheb V. ; Apata, Ikeoluwa E. ; Pradhan, Nihar ; Karim, Alamgir ; Raghavan, Dharmaraj ( May 2021 , Molecules)

   null (Ed.)

   The synthesis of polymer-grafted nanoparticles (PGNPs) or hairy nanoparticles (HNPs) by tethering of polymer chains to the surface of nanoparticles is an important technique to obtain nanostructured hybrid materials that have been widely used in the formulation of advanced polymer nanocomposites. Ceramic-based polymer nanocomposites integrate key attributes of polymer and ceramic nanomaterial to improve the dielectric properties such as breakdown strength, energy density and dielectric loss. This review describes the ”grafting from” and ”grafting to” approaches commonly adopted to graft polymer chains on NPs pertaining to nano-dielectrics. The article also covers various surface initiated controlled radical polymerization techniques, along with templated approaches for grafting of polymer chains onto SiO2, TiO2, BaTiO3, and Al2O3 nanomaterials. As a look towards applications, an outlook on high-performance polymer nanocomposite capacitors for the design of high energy density pulsed power thin-film capacitors is also presented. 

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