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Title: The Role of Carbon Content: A Comparison of the Nickel Particle Size and Magnetic Property of Nickel/Polysiloxane‐Derived Silicon Oxycarbide
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Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Engineering Materials
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    In this study, novel ferromagnetic Ni‐containing silicon oxycarbide (SiOC–Ni) was successfully fabricated from a base polysiloxane (PSO) with the addition of nickel 2,4‐pentanedionate. The resultant SiOC–Ni nanocomposite consists of in situ formed Ni nanocrystallites with a small amount of NiO uniformly dispersed in the amorphous SiOC matrix, and the corresponding nanocrystallite size increases with the increase of the pyrolysis temperature. The formation of nickel silicides (NixSiy) is completely suppressed by the effect of water vapor during the pyrolysis. The fundamental phase evolution process and mechanisms are explained. In an argon atmosphere, the SiOC–Ni materials pyrolyzed at 900°C are stable up to 1000°C with less than 6 wt% weight loss; they exhibit desirable electrical conductivity up to ~900°C with the highest electrical conductivity at ~247 S/m. This series of SiOC–Ni materials also demonstrates exciting ferromagnetic behaviors. Their new semiconducting behavior with soft ferromagnetism presents promising application potentials for magnetic sensors, transformers, actuators, etc.

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  2. Abstract

    In this study, silicon oxycarbide (SiOC) is selected as the base polymer to derive a SiOC ceramic (PDC) matrix, and four transition metals M (M = Ni, Mo, Co, and Zr) are individually introduced into the SiOC base to form various SiOC/M systems. SiOC‐Ni, SiOC‐MoCx, and SiOC‐CoSixare obtained by pyrolysis at 1100°C, whereas SiOC‐ZrOxforms upon pyrolysis at 1400°C. The selected SiOC/M systems encompass four different types of phase separation pathways—pure metal, metal carbide, metal silicide, and metal oxide (SiC‐SiO2‐C‐Ni, SiC‐SiO2‐C‐MoCx, SiC‐SiO2‐C‐CoSix, and SiC‐SiO2‐C‐ZrOx). The driving force for crystallization has been analyzed using a Gibbs free energy minimization method and phase fractions of these different PDC systems are calculated based on the lever rule. This work also reveals the energetics related to the quaternary systems and provides guidance to synthesizing metal‐containing PDCs with desired phase contents. In addition, we have examined the broad applicability of the phase content prediction method for a variety of other SiOC/M systems.

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    Transition metal chalcogenide nanoparticles (NPs) are of interest for energy applications, including batteries, supercapacitors, and electrocatalysis. Many methods have been established for synthesizing Ni NPs, and conversion chemistry to form Ni oxide and phosphides from template Ni NPs is well‐understood. Sulfidation and selenidation of Ni NPs have been much less explored, however. We report a method for the conversion of Ni template NPs into sulfide and selenide product NPs using elemental sulfur, 1‐hexadecanthiol, thiourea, trioctylphosphine sulfide, elemental selenium, and selenourea. While maintaining mole ratios of 2 mmol sulfur/selenium precursor: mmol Ni, products with phases of Ni3S2, Ni9S8, NiS, NiSO4·6H2O, Ni3S4, Ni3Se2, and NiSe have been obtained. The products have voids that form through the Kirkendall effect during interdiffusion. Trends relating the chemical properties of the precursors to the phases of the products have been identified. While some precursors contained phosphorus, there was no significant incorporation of phosphorus in any of the products. An increase of the NP size during sulfidation and selenidation is consistent with ripening. The application of Ni sulfide and selenide NPs as electrocatalysts for the hydrogen evolution reaction is also demonstrated.

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  4. Abstract

    Although processing via external stimuli is a promising technique to tune the structure and properties of polymeric materials, the impact of magnetic fields on phase transitions in thermoresponsive polymer solutions is not well‐understood. As nanoparticle (NP) addition is also known to impact these thermodynamic and optical properties, synergistic effects from combining magnetic fields with NP incorporation provide a novel route for tuning material properties. Here, the thermodynamic, optical, and rheological properties of aqueous poly(N‐isopropyl acrylamide) (PNIPAM) solutions are examined in the presence of hydrophilic silica NPs and magnetic fields, individually and jointly, via Fourier‐transform infrared spectroscopy (FTIR), magneto‐turbidimetry, differential scanning calorimetry (DSC), and magneto‐rheology. While NPs and magnetic fields both reduce the phase separation energy barrier and lower optical transition temperatures by altering hydrogen bonding (H‐bonding), infrared spectra demonstrate that the mechanism by which these changes occur is distinct. Magnetic fields primarily alter solvent polarization while NPs provide PNIPAM–NP H‐bonding sites. Combining NP addition with field application uniquely alters the solution environment and results in field‐dependent rheological behavior that is unseen in polymer‐only solutions. These investigations provide fundamental understanding on the interplay of magnetic fields and NP addition on PNIPAM thermoresponsivity which can be harnessed for increasingly complex stimuli‐responsive materials.

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