• 제목/요약/키워드: Polymer assembly

검색결과 268건 처리시간 0.023초

광화학적 가스 센싱을 위한 광변색 스피로피란 개질된 유기-무기 하이브리드 메조포러스 실리카 (Photochromic Spiropyran-Functionalized Organic-Inorganic Hybrid Mesoporous Silica for Optochemical Gas Sensing)

  • 박성수;하창식
    • 접착 및 계면
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    • 제17권4호
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    • pp.141-148
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    • 2016
  • 본 연구에서는 트리블럭 공중합체($PEO_{20}PPO_{70}PEO_{20}$, P123)를 주형으로 사용하고 테트라에틸오르소실리케이트(Tetraethyl orthosilicate, TEOS)를 실리카원으로 사용하여 산 조건 하에서 자기조립 과정을 거친 후 메조포러스 실리카(SBA-15)를 합성하였다. SBA-15는 높은 표면적($704m^2g^{-1}$), 균일한 나노세공(8.4 nm) 그리고 잘 배열된 육방체 구조를 가진다. 스피로피란(Spiropyran) 기가 개질된 SBA-15 (Spiropyran-SBA-15)는 3-(트리에톡시실릴)프로필 이소시아네이트(TESPI)와1-(2-하이드록시에틸)-3,3-이메틸인돌리노-6'-니트로벤조프릴로스피렌(HDINS)을 이용하여 SBA-15에 후처리하여 합성하였다. Spiropyran-SBA-15는 개질 후 나노세공 구조의 손상없이 잘 배열된 육방체 구조를 가졌다. 그리고 표면적과 세공 크기는 각각 $651m^2g^{-1}$와 8.0 nm이었다. 그리고 다양한 화학 기체(EtOH, THF, $CHCl_3$, Acetone, HCl)를 이용하여 Spiropyran-SBA-15의 광화학적 특성을 연구하였다. 유기분자 기체들(EtOH, THF, $CHCl_3$, Acetone)에 대한 광 형광 스펙트라의 주요 발광 피크는 603.4 nm부터 592.1 nm까지 blue shift하였다. 피크 세기는 0.8부터 0.3까지 감소하였다. Spiropyran-SBA-15시료를 HCl 기체에 노출한 후 측정한 광 형광 스펙트럼은 현저한 blue shift를 보여주었다. 광 형광 스펙트럼은 592.1 nm까지 이동하였다. 또한, 광 형광 스펙트럼의 정규화된 피크 세기는 0.1까지 감소하였다.

D-$\Pi$-A designed dye chromophores and nanoparticles: optical properties, chemosensor effects and PE/Aramid fiber colorations

  • Son, Young-A;Kim, Su-Ho;Kim, Young-Sung
    • 한국염색가공학회:학술대회논문집
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    • 한국염색가공학회 2010년도 제3회 국제학회
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    • pp.40-40
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    • 2010
  • Studies on attractive color changing property of dye chromophore and fluorophore have been greatly enjoyed in the related industrial and research fields such as optoelectronics, chemosensor, biosensor and so on. The optical property based on D-$\Pi$-A intramolecular charge transfer (ICT) system of chromophore molecules can be utilized as suitable sensing probes for checking media polarity and determining colorimetric chemosensing effect, especially heavy metal detection. These finding are obtained by absorption and emission properties. In this work, donor-acceptor D-$\Pi$-A type fluorescent dyes were designed and synthesized with the corresponding donor and acceptor groups. The selected donor moieties might be provided prominent amorphous properties which are very useful in designing and synthesizing functional polymers and in fabricating devices. Another reasons to choose are commercial availabilities in high purity and low price. Donor-bridge-acceptor (D-A) type dyes can produce impressive optical-physical properties, yielding them potentially suitable for applications in the synthesis of small functional organic molecules. Small organic functional molecules have unique advantages, such as better solubility, amorphous character, and represent an area of research which needs to be explored and developed. Currently, their applications in metalorganic compounds is rapidly expanding and becoming widespread in self-assembly processes, photoluminescence applications, chiral organocatalysts, and ingrafts with nanomaterials. Colloidal nanoparticles have received great attentions in recent years. The photophysical properties of nanoparticles, particularly in terms of brightness, photostability, emission color purity and broad adsorption range, are very attractive functions in many applications. To our knowledge background, colloidal nanoparticles have been enjoyed their applications in bio-probe research fields. This research interest can be raised by the advantages of the materials such as high photoluminescence quantum yields, sharp emission band, long-term photostability and broad excitation spectra. In recent, the uses of nanoparticles being embedded in a polymer matrix and binded on polymer surface have been explored and their properties such as photo-activation and strong photoluminescence have been proposed. The prepared chromophores and nanoparticles were investigated with absorption and emission properties, solvatochromic behaviors, pH induced color switching effects, chemosensing effects and HOMO/LUMO energy potentials with computer simulation. In addition, synthesized fluorophore dyes and particles were applied onto PE/Aramid fiber fluorescing colorations. And the related details were then discussed.

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후코이단과 탄닌산에 의한 PEMFC 고분자막의 내구성 향상 (Enhancement of Membrane Durability in PEMFC by Fucoidan and Tannic Acid)

  • 이미화;오소형;추천호;김영숙;나일채;박권필
    • Korean Chemical Engineering Research
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    • 제61권1호
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    • pp.45-51
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    • 2023
  • PEMFC(고분자전해질 연료전지) 고분자막의 내구성을 향상시키기 위해서 라디칼 제거제와 지지체가 사용되고 있다. 본 연구에서는 화학적 내구성과 물리적 내구성을 향상시키기 위해서 해조류에서 추출한 후코이단과 가교제 역할을 하는 탄닌산을 첨가한 고분자막의 내구성을 평가하였다. 물리적 내구성은 인장강도를 측정해 확인했고, 화학적 내구성은 Fenton 실험으로 측정하였다. 막과 전극합체(MEA)를 제조하여 셀에서 가속 내구 평가를 통해 기계적 내구성과 화학적 내구성을 평가하였다. 인장강도 측정으로 후코이단과 탄닌산의 변형율과 항복강도 등을 향상시켜 고분자막의 기계적 내구성을 향상시킬 수 있음을 보였다. 후코이단이 라디칼 제거제 역할을 함을 Fenton 실험에서 확인했다. 단위전지에서 가속 내구 실험 결과 후코이단은 화학적 내구와 기계적 내구를 모두 향상시켜 무첨가막보다 가속 내구 평가 시간을 38.1% 증가시켰고, 탄닌산을 추가하면 기계적 내구성 향상에 의해 고분자막의 내구성이 13.9% 향상되었다.

PEMFC에서 Pt-Co/C Cathode 촉매가 고분자막의 전기화학적 내구성에 미치는 영향 (Effect of Pt-Co/C Cathode Catalyst on Electrochemical Durability of Membrane in PEMFC)

  • 오소형;유동근;김명환;박지용;박권필
    • Korean Chemical Engineering Research
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    • 제61권2호
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    • pp.189-195
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    • 2023
  • PEMFC(고분자 전해질 막 연료전지) cathode 촉매로 Pt-Co/C가 내구성 향상 때문에 최근에 많이 사용되는 추세이다. 연료전지에서 전극과 전해질은 상호 간에 성능과 내구성 면에서 밀접하게 영향을 준다. Pt/C 전극 촉매에서 Pt-Co/C로 대체되었을 때 고분자 전해질막의 전기화학적 내구성에 미치는 영향에 대해서 연구하였다. PEMFC 고분자막의 전기화학적 가속 열화 과정에서 Pt-Co/C MEA(막전극접합체)의 내구성이 Pt/C MEA 내구성보다 높았다. FER (불소유출속도)와 수소투과도를 분석한 결과 Pt-Co/C MEA의 고분자막 열화속도가 Pt/C MEA보다 낮음을 보였다. OCV(개회로전압) holding 과정에서 Pt-Co/C 전극의 활성면적 감소속도가 Pt/C 전극보다 낮고, 고분자막에 석출되는 Pt 양도 Pt-Co/C MEA가 Pt/C MEA보다 작았다. 고분자막 내부의 Pt는 라디칼을 생성해서 고분자막을 열화시킴으로 Pt 석출 속도가 높은 Pt/C MEA의 고분자막 열화속도가 높게 나타났다. Pt-Co/C 촉매를 사용하면 전극 내구성도 향상되고, 고분자막에 석출되는 Pt양도 감소해서 고분자막의 전기화학적 내구성을 향상시켰다.

고분자연료전지의 화학적/기계적 내구성 평가 시간 단축 (Reducing the Test Time for Chemical/Mechanical Durability of Polymer Electrolyte Membrane Fuel Cells)

  • 오소형;유동근;김명환;박지용;최영진;박권필
    • Korean Chemical Engineering Research
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    • 제61권4호
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    • pp.517-522
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    • 2023
  • 고분자전해질 연료전지 (PEMFC)에 공기와 수소를 공급하고 개회로전압 (OCV) 상태에서 가습/건조를 반복하는 고분자막의 화학적/기계적 내구성 평가법이 사용되고 있다. 이 프로토콜에서 가습/건조가 반복되면 전압 상승/감소가 반복되어 전극 열화도 발생한다. 막 내구성이 우수한 경우 전압 변화 횟수가 증가해, 전극 열화에 의해 평가가 종료되어 원래 목적인 막 내구성 평가를 할 수 없는 문제가 발생하기도 한다. 본 연구에서는 미국 에너지부 (DOE)와 동일한 프로토콜을 사용하되 cathode 가스로 공기대신 산소를 사용하고 가습/건조시간과 유량도 증가시켜 막의 화학적/기계적 열화 속도를 증가시켜서 고분자막 내구 평가 시간을 단축시킴으로서 이와 같은 문제를 개선하고자 하였다. Nafion 211 막전극접합체(MEA) 내구성 평가를 공기 대신 산소를 사용해서 가속화도를 2.6배 증가시켜 2,300 사이클만에 평가 종료하였다. 본 프로토콜에 의해 고분자막도 가속 열화되고, 전극 촉매도 가속 열화되어 고분자막과 전극의 내구성을 동시에 평가할 수 있는 이점도 있었다.

Self-assembly Coordination Compounds of Cu(II), Zn(II) and Ag(I) with btp Ligands (btp = 2,6-bis(N'-1,2,4-triazolyl)pyridine):Counteranion Effects

  • Kim, Cheal;Kim, Sung-Jin;Kim, Young-Mee
    • 한국결정학회지
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    • 제16권2호
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    • pp.107-127
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    • 2005
  • Five Cu(II) compounds were obtained from different copper salts with btp ligands, and their structures were determined by X-ray crystallography. The structure of coordination polymer 2 contains btp-bridged tetranuclear Cu(II) units weakly connected by nitrate ions, and the structure of a discrete Cu(II) molecule 1 contains acetates and btp ligands. With perchlorate anions, two btp ligands bridge Cu(II) ions to form a double zigzag chain 3, while a single zigzag chain 4 is created with sulfate anions. The reaction of $Cu(NO_{3})_{2}$ containing $NH_{4}PF_{6}$ with btp ligands also produced a polymeric compound 5 containing $Cu(H_{2}O)_{2}^{2+}$ and $Cu(NO_{3})_{2}$ units alternatively bridged by btp ligands with H-bonds between copper bonded water and nitrate oxygen atoms. Five Zn(II) compounds were obtained from different zinc salts with btp ligands, and the structures of polymeric compounds (6, 7 and 8) and monomeric compounds (9 and 10) were determined by X-ray crystallography. With nitrate, chloride and bromide anions, btp ligands bridge Zn(II) ions to form polymeric compounds (6, 7 and 8), but btp ligands coordinate to a Zn(II) ion to form monomeric complexes (9 and 10) with $PF_{6}^{-}$ and perchlorate anions. Four silver salts and btp ligands produced two kinds of structures, dinuclear 20-membered rings and one-dimensional zigzag chain depending on different anions. For $ClO_{4}^{-}$ and OTf anions, weak interactions between Ag(I) and anions make dinuclear 20-membered rings construct polymeric compounds (11 and 13). For $PF_{6}^{-}$ anion, there are also weak interactions between Ag(I) and $F(PF_{6}^{-})(12)$, but they do not construct a polymeric compound. For $O_{2}CCF_{3}^{-}$ anion, btp ligands bridge Ag(I) atoms to make one-dimensional zigzag chain (14), and there are also interactions between Ag(I) and anions.

Chemoenzymatic Synthesis of Dual-responsive Amphiphilic Block Copolymers and Drug Release Studies

  • Chen, Peng;Li, Ya-Peng;Wang, Shu-Wei;Meng, Xin-Lei;Zhu, Ming;Wang, Jing-Yuan
    • Bulletin of the Korean Chemical Society
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    • 제34권6호
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    • pp.1800-1808
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    • 2013
  • Dual-responsive amphiphilic block copolymers were synthesized by combining enzymatic ring-opening polymerization (eROP) of ${\varepsilon}$-caprolactone (CL) and ATRP of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA). The obtained block copolymers were characterized by gel permeation chromatography (GPC), $^1H$ NMR and FTIR-IR. The critical micelle concentration (CMC) of copolymer was determined by fluorescence spectra, it can be found that with hydrophilic block (PDMAEMA) increasing, CMC value of the polymer sample increased accordingly, and the CMC value was 0.012 mg/mL, 0.025 mg/mL and 0.037 mg/mL for $PCL_{50}$-b-$PDMAEMA_{68}$, $PCL_{50}$-b-$PDMAEMA_{89}$, $PCL_{50}$-b-$PDMAEMA_{112}$, $PCL_{50}$-b-$PDMAEMA_{89}$ was chosen as drug carrier to study in vitro release profile of anti-cancer drug (taxol). The temperature and pH dependence of the values of hydrodynamic diameter (Dh) of micelles, and self-assembly of the resulting block copolymers in water were evaluated by dynamic light scattering (DLS). The result showed that with the temperature increasing and pH decreasing, the Dh decreased. Drug-loaded nanoparticles were fabricated using paclitaxel as model. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) had been explored to study the morphology of the hollow micelles and the nanoparticles, revealing well-dispersed spheres with the average diameters both around 80 nm. In vitro release kinetics of paclitaxel from the nanoparticles was also investigated in different conditions (pH and temperature, etc.), revealing that the drug release was triggered by temperature changes upon the lower critical solution temperature (LCST) at pH 7.4, and at $37^{\circ}C$ by an increase of pH.

Fluctuation in Plasma Nanofabrication

  • Shiratani, Masaharu
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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    • pp.96-96
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    • 2016
  • Nanotechnology mostly employs nano-materials and nano-structures with distinctive properties based on their size, structure, and composition. It is quite difficult to produce nano-materials and nano-structures with identical sizes, structures, and compositions in large quantities, because of spatiotemporal fluctuation of production processes. In other words, fluctuation is the bottleneck in nanotechnology. We propose three strategies to suppress such fluctuations: employing 1) difference between linear and nonlinear phenomena, 2) difference in time constants, and 3) nucleation as a bottleneck phenomenon. We are also developing nano- and micro-scale guided assembly using plasmas as a plasma nanofabrication.1-5) We manipulate nano- and micro-objects using electrostatic, electromagnetic, ion drag, neutral drag, and optical forces. The accuracy of positioning the objects depends on fluctuation of position and energy of an object in plasmas. Here we evaluate such fluctuations and discuss the mechanism behind them. We conducted in-situ evaluation of local plasma potential fluctuation using tracking analysis of fine particles (=objects) in plasmas. Experiments were carried out with a radio frequency low-pressure plasma reactor, where we set two quartz windows at the top and bottom of the reactor. Ar plasmas were generated at 200 Pa by applying 13.56MHz, 450V peak-to-peak voltage. The injected fine particles were monodisperse methyl methacrylate-polymer spheres of $10{\mu}m$ in diameter. Fine particles were injected into the reactor and were suspended around the plasma/sheath boundary near the powered electrode. We observed binary collision of fine particles with a high-speed camera. The frame rate was 1000-10000 fps. Time evolution of their distance from the center of mass was measured by tracking analysis of the two particles. Kinetic energy during the collision was obtained from the result. Potential energy formed between the two particles was deduced by assuming the potential energy plus the kinetic energy is constant. The interaction potential is fluctuated during the collision. Maximum amplitude of the fluctuation is 25eV, and the average is 8eV. The fluctuation can be caused by neutral molecule collisions, ion collisions, and fluctuation of electrostatic force. Among theses possible causes, fluctuation of electrostatic force may be main one, because the fine particle has a large negative charge of -17000e and the corresponding electrostatic force is large compared to other forces.

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수전해 반응에 의한 고분자전해질 연료전지 전극과 막의 열화 (Degradation of Electrode and Membrane in Proton Exchange Membrane Fuel Cell After Water Electrolysis)

  • 정재현;신은경;정재진;나일채;추천호;박권필
    • Korean Chemical Engineering Research
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    • 제52권6호
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    • pp.695-700
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    • 2014
  • 고분자전해질 연료전지로 물을 전기분해하여 수소와 산소를 발생시킬 수 있다. 그러나 1.7V 이상의 높은 전압에서 수전해 반응이 일어나므로 전극과 고분자 전해질 막의 열화가 빠르게 진행된다. 수전해 과정에서 anode의 열화를 방지하기 위해 촉매로 지지체 없는 $IrO_2$를 보통 사용하는데 본 연구에서는 고분자전해질 연료전지용 Pt/C 촉매를 수전해 반응에 그대로 사용했을 때 전극과 막의 열화 현상을 분석하였다. 1.8~2.0 V 전압 범위에서 수전해 반응 후 고분자 전해질 연료전지 구동 조건에서 I-V, CV, 임피던스, LSV를 측정했다. 수전해 전압이 높을수록 전극과 막의 열화 속도가 증가하였다. 2.0 V에서 1분 동안 수전해 반응했을 때 수소 수율은 88%였고, 전극과 고분자 막이 열화되어 0.6 V에서 성능이 49% 감소하였다.

고분자전해질 연료전지 내구성 향상을 위한 시동 기술 개발에 관한 연구 (Development of a Durable Startup Procedure for PEMFCs)

  • 김재홍;조유연;장종현;김형준;임태훈;오인환;조은애
    • 한국신재생에너지학회:학술대회논문집
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    • 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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    • pp.288-294
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    • 2009
  • Various polymer electrolyte membrane fuel cell (PEMFC) startup procedures were tested to explore possible techniques for reducing performance decay and improving durability during repeated startup-shutdown cycles. The effects of applying a dummy load, which prevents cell reversal by consuming the air at the cathode, on the degradation of a membrane electrode assembly (MEA) were investigated via single cell experiments. The electrochemical results showed that application of a dummy load during the startup procedure significantly reduced the performance decay, the decrease in the electrochemically active surface area (EAS), and the increase in the charge transfer resistance ($R_{ct}$), which resulted in a dramatic improvement in durability. After 1200 startup-shutdown cycles, post-mortem analyses were carried out to investigate the degradation mechanisms via various physicochemical methods including FESEM, an on-line $CO_2$ analysis, EPMA, XRD, FETEM, SAED, FTIR. After 1200 startup-shutdown cycles, severe Pt particle sintering/agglomeration/dissolution and carbon corrosion were observed at the cathode catalyst layer when starting up a PEMFC without a dummy load, which significantly contributed to a loss of Pt surface area, and thus to cell performance degradation. However, applying a dummy load during the startup procedure remarkably mitigated such severe degradations, and should be used to increase the durability of MEAs in PEMFCs. Our results suggest that starting up PEMFCs while applying a dummy load is an effective method for mitigating performance degradation caused by reverse current under a repetition of unprotected startup cycles.

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