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    Reusability, Long-Life Storage and Highly Sensitive Zirconium Nitride (ZrN) Surface-Enhanced Raman Spectroscopy (SERS) Substrate Fabricated by Reactive Gas-Timing Rf Magnetron Sputtering
    (2023-12-22)
    Sucheewa, Nguentra
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    Wongwiriyapan, Winadda
    ;
    Rattanawarinchai, Prapakorn
    ;
    Wuttikhun, Tuksadon
    ;
    Sinthiptharakoon, Kittiphat
    Transition metal nitrides (TMN) are promising material alternative to replace noble metals in the field of plasmonic applications, especially surface-enhanced Raman spectroscopy (SERS). Here we demonstrate a practical surface enhanced Raman spectroscopy (SERS) substrate using zirconium nitride (ZrN) thin films grown by reactive gas-timing (RGT) rf magnetron sputtering. The tailored properties of ZrN thin film exploited for SERS activity could be achieved to obtain a highly sensitive ZrN thin film SERS substrate with the enhancement factor (EF) of 1.24 × 106 and 4.8 %RSD at 1626 cm-1 toward methylene blue (MB) analyte which are comparable to the optimized Au sputtered thin films (EF=1.18 × 106 and with 5.1%RSD). We find that the spatial plasmonic hotspots on the surface of ZrN SERS substrate controlled by the turn-on timing of Ar:N2 sputtered gas sequence, leading to the discrete conductive surface profile, strongly relates to non-stoichiometric composition and the degree of (200)-oriented texture at the surface of ZrN thin film. Furthermore, ZrN thin film SERS substrates exhibit an excellent recyclability more than 30 cycles with simple cleaning process and a storage time longer than 6 months. The detection and reusability of ZrN SERS substrate on the low concentration of trinitrotoluene (TNT) for homeland security are also performed.
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    Carbon nanotube/polydimethylsiloxane composite micropillar arrays using non-lithographic silicon nanowires as a template for performance enhancement of triboelectric nanogenerators
    (2021-02-26)
    Pinming, Chinathun
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    Wongwiriyapan, Winadda
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    Rattanamai, Songsak
    ;
    Ketama, Nathakreat
    ;
    Treetong, Alongkot
    Carbon nanotube/polydimethylsiloxane composite micropillar (CNT/PDMS MP) arrays were successfully fabricated using non-lithographic silicon nanowire (SiNW) arrays as a template for performance enhancement of triboelectric nanogenerators (TENG). The CNT/PDMS MP arrays were obtained by pouring CNT/PDMS composites on the SiNW arrays and peeled off. Surface topology of CNT/PDMS composites directly depends on morphology of SiNW arrays, which can be varied by the etching time of the typical metal-assisted chemical etching process. The micropatterned CNT/PDMS composites was mostly depicted to the SiNW array template pattern when the morphologies of the SiNW were optimized with a length of approximately 10 mm. Next, the CNT/PDMS MP arrays were utilized as a triboelectric layer of TENGs, generating the maximum output voltage of 22.84 0.85 V, enabling an approximately 18-fold improvement in an electrical output compared to the flat PDMS-based TENG. The performance enhancement of TENGs based on CNT/PDMS MP arrays are attributed to synergic effects of (1) an enhancement of electrostatic induction by CNT composites, increasing dielectric constant, and (2) an enhancement of electrification by surface texturing using non-lithographic pattern and CNT composites.
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    Efficiency of SPIONs functionalized with polyethylene glycol bis(amine) for heavy metal removal
    (2016-09-15)
    Wanna, Yongyuth
    ;
    Chindaduang, Anon
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    Tumcharern, Gamolwan
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    Phromyothin, Darinee
    ;
    Porntheerapat, Supanit
    Hybrid magnetic nanoparticles based on poly(methylmethacrylate) (PMMA) and super-paramagnetic iron oxide nanopaticles (SPIONs) with selective surface modification has been developed for heavy metal removal by applying external magnetic fields. The nanoparticles were prepared by the emulsion polymerization technique in an aqueous suspension of SPIONs. The hydrolysis of carboxyl functional group was then applied for grafting polyethylene glycol bis(amine)(PEG-bis(amine)) onto the PMMA-coated SPIONs. The morphology, the chemical structure and the magnetic properties of the grafted nanoparticles were investigated. The efficiency of the hybrid nanoparticles for heavy metal removal were conducted on Pb(II), Hg(II), Cu(II) and Co(II) in aqueous solutions.The metal concentration in the solutions after separation by the hybrid nanoparticles was determined by inductively coupled plasma optical emission spectrometer (ICP-OES). The results show the heavy metal uptake ratios of 0.08, 0.04, 0.03, and 0.01 mM per gramme of the grafted SPIONs for Pb(II), Hg(II), Cu(II), and Co(II), respectively. A competitive removal of Cu(II), Pb(II), Co(II) and Hg(II) ions in mixed metal salt solutions has also been studied.The heavy metal removal efficiency of the hybrid nanoparitcles was found to depend on the cation radius, in accordance with capture of metal ions by the amine group.
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    Preparation and characterization of PEG bis(amine) grafted PMMA/SPION composite nanoparticles
    (2016-03-01)
    Wanna, Yongyuth
    ;
    Pui-ngam, Rachineewan
    ;
    Nukeaw, Jitti
    ;
    Chindaduang, Anon
    ;
    Tumcharern, Gamolwan
    We report novel magnetic composite nanoparticles for heavy metal ion separation. Superparamagnetic iron oxide nanoparticles (SPIONs) and were coated with poly(methylmethacrylate) (PMMA) by emulsion polymerization process in the aqueous suspension of SPIONs. In addition, the hydrolysis of carboxylic functional groups onto the PMMA-coated SPIONs was grafted with Polyethylene glycol bis(amine). Then, the functional group structures were investigated by Fourier transforms infrared spectroscopy (FTIR). The morphology of PMMA/SPIONs was determined by transmission electron microscopy (TEM) and atomic force microscope (AFM). The magnetic property was investigated by the vibrating sample magnetometer (VSM). The metal concentration in the solution after separation using the nanoparticles was determined by inductivity coupled plasma optical emission spectrometer (ICP-OES). Furthermore, we demonstrate that the efficiencies of the heavy metal ion removal for Cu(II), Mn(II), Zn(II), Cd(II), Pb(II), Co(II) and Ni(II) are 80.0%, 57.7%, 54.3%, 40.0%, 34.8%, 32.5% and 30.2% by weight, respectively. The nanoparticles also exhibit some selectivity for copper, manganese and zinc. The results show that the composite nanoparticles are extremely promising for heavy metal ion separation.
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    Heavy metal detection by electrochemical electronic tongue with poly(thiophene)-metal oxide nanoparticle composite electrodes
    (2011-12-01)
    Saeteaw, Kanjana
    ;
    Tumcharern, Gamolwan
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    Piyakulawat, Phimwipha
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    Asawapirom, Udom
    ;
    Porntheeraphat, Supanit
    Rapid monitoring methods of heavy metals in water are in great demand for industrial environmental managements. This work aims to develop a heavy metal sensing device based on an electrochemical electronic tongue using a hybrid composite of metal oxide nanoparticles and conductive polymer as the working electrodes. The electrodes were prepared by drop-casting colloidal mixtures of Regioregular poly(3-hexylthiophene) (P3HT) and metal oxide nanoparticles (ZnO or TiO <inf>2</inf>) in chloroform onto a fluorine-doped tin oxide (FTO) glass. Optical microscopy measurements reveal some microstructural organization of the metal oxide-P3HT composite films on the electrodes, in comparison to a smooth P3HT film. Cyclic voltammetry (CV) measurements using bare FTO, P3HT, P3HT/ZnO and P3HT/TiO <inf>2</inf> electrodes were performed on aqueous solutions of various metal acetates at the concentration of 0.01M. The Principal Component Analysis (PCA) was applied to the CV results to obtain the classification of the data from the various metal salt solutions. The PCA score plot exhibits a clear separation of the data groups of different heavy metals, with the highest distinction between zinc and lead. The PCA loading plot confirms that the different electrochemical nature of the various electrodes is responsible for such distinctive classification. Further work is to examine the capability of the electrochemical electronic tongues for semi-quantitative analyses of the metal salt concentration. © 2011 IEEE.