• Polymer(Korea)
• /
• v.36 no.6
• /
• pp.693-698
• /
• 2012

In this study aluminum isopropyl oxide ($Al(O-i-Pr)_3$) was supported on the amine-functionalized surface of silica to synthesize high molecular weight (MW) polylactide (PLA), and it was tested for PLA polymerization behaviors. A silica was funtionalized with silane compound having amine groups, then in-situ treated with $Al(O-i-Pr)_3$. $Al(O-i-Pr)_3$ attached to amine group on silica showed activity only in the presence of MAO (methyl aluminoxane). At the polymerization temperature of $115^{\circ}C$, the conversion and the MW of PLA were increased as the amount of silane was increased. At the polymerization temperature of $130^{\circ}C$, the conversion was decreased while the MW was increased drastically and reached to MW 44000 g/mol when the amine concentration was 3.0 mmol/g. A bimodal type GPC curve was shown at the polymerization temperature of $115^{\circ}C$. As the amount of amine group increased, the peaks of GPC curve were merged. At the polymerization of $130^{\circ}C$, a unimodal GPC curve was shown. $Al(O-i-Pr)_3$ supported on amine-functionalized silica was able to produce higher MW PLA with enhanced activity compared to homogeneous $Al(O-i-Pr)_3$.

• Clean Technology
• /
• v.23 no.3
• /
• pp.308-313
• /
• 2017

In this study, we investigated the electrocatalytic effects of the N and O co-doping of Graphite Felt (GF) electrode for the vanadium redox flow battery (VRFB) at the cathode and the anode reaction, respectively. The electrodes were prepared by chemical vapor deposition (CVD) with $NH_3-O_2$ at 773 K, and its effects were compared with an electrode prepared by an O doping treatment. The surface morphology and chemical composition of the electrodes were characterized by scanning electron microscopy (SEM) and photoelectron spectroscopy (XPS). The electrocatalytic properties of these electrodes were characterized in a VRFB single cell comparing the efficiencies and performance of the electrodes at the cathode, anode, and single cell level. The results exhibited about 2% higher voltage and energy efficiencies on the N-O-GF than the O-GF electrode. It was found that the N and O co-doping was particularly effective in the enhancement of the reduction-oxidation reaction at the anode.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.02a
• /
• pp.17-18
• /
• 2011

Plasma in liquid phase has attracted great attention in the last few years by the wide domain of applications in material processing, decomposition of organic and inorganic chemical compounds and sterilization of water. The plasma in liquid is characterized by three main regions which interact each - other during the plasma operation: the liquid phase, which supply the plasma gas phase with various chemical compounds and ions, the plasma in the gas phase at atmospheric pressure and the interface between these two regions. The most complex region, but extremely interesting from the fundamental, chemical and physical processes which occur here, is the boundary between the liquid phase and the plasma gas phase. In our laboratory, plasma in liquid which behaves as a glow discharge type, is generated by using a bipolar pulsed power supply, with variable pulse width, in the range of 0.5~10 ${\mu}s$ and 10 to 30 kHz repetition rate. Plasma in water and other different solutions was characterized by electrical and optical measurements. Strong emissions of OH and H radicals dominate the optical spectra. Generally water with 500 ${\mu}S/cm$ conductivity has a breakdown voltage around 2 kV, depending on the pulse width and the repetition rate of the power supply. The characteristics of the plasma initiated in ultrapure water between pairs of different materials used for electrodes (W and Ta) were investigated by the time-resolved optical emission and the broad-band absorption spectroscopy. The deexcitation processes of the reactive species formed in the water plasma depend on the electrode material, but have been independent on the polarity of the applied voltage pulses. Recently, Coherent anti-Stokes Raman Spectroscopy method was employed to investigate the chemistry in the liquid phase and at the interface between the gas and the liquid phases of the solution plasma system. The use of the solution plasma allows rapid fabrication of the metal nanoparticles without being necessary the addition of different reducing agents, because plasma in the liquid phase provides a reaction field with a highly excited energy radicals. We successfully synthesized gold nanoparticles using a glow discharge in aqueous solution. Nanoparticles with an average size of less than 10 nm were obtained using chlorauric acid solutions as the metal source. Carbon/Pt hybrid nanostructures have been obtained by treating carbon balls, synthesized in a CVD chamber, with hexachloro- platinum acid in a solution plasma system. The solution plasma was successfully used to remove the template remained after the mesoporous silica synthesis. Surface functionalization of the carbon structures and the silica surface with different chemical groups and nanoparticles, was also performed by processing these materials in the liquid plasma.

• Polymer(Korea)
• /
• v.39 no.1
• /
• pp.169-173
• /
• 2015

Metallocene was supported on the silica, which was functionalized with aminosilanes such as aminopropyltrimethoxysilane (1NS) or N-[3-(trimethoxysilyl)propyl]ethylenediamine (2NS), and ionic liquids such as 1-butyl-4-methylpyridinium chloride (Cl), tributylmethylammonium chloride (Amm), benzyldimethyltetradecylammonium chloride (Ben), 1-butyl-1-methylpyrrolidinium chloride (Pyr), and then ethylene polymerizations were performed. The Zr contents of $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ and $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ were lower than those of only aminosilane-treated silicas. However, the polymerization activity of $SiO_2/1NS/IL/(n-BuCp)_2ZrCl_2$ was higher than that of $SiO_2/1NS/(n-BuCp)_2ZrCl_2$. The polymerization activity of $SiO_2/2NS/IL/(n-BuCp)_2ZrCl_2$ was lower than that of $SiO_2/2NS/(n-BuCp)_2ZrCl_2$ due to much lower Zr content.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2012.08a
• /
• pp.400-401
• /
• 2012

그래핀(Graphene)은 열 전도도가 높고 전자 이동도(200 000 cm2V-1s-1)가 우수한 전기적 특성을 가지고 있어 전계 효과 트랜지스터(Field effect transistor; FET), 유기 전자 소자(Organic electronic device)와 광전자 소자(Optoelectronic device) 같은 반도체 소자에 응용 가능하다. 그러나 에너지 밴드 갭이 없기 때문에 소자의 전기적 특성이 제한되는 단점이 있다. 최근에는 아크 방출(Arc discharge method), 화학적 기상 증착법(Chemical vapor deposition; CVD), 이온-조사법(Ion-irradiation) 등을 이용한 이종원자(Hetero atom)도핑과 화학적 처리를 이용한 기능화(Functionalization) 등의 방법으로 그래핀을 도핑 후 에너지 밴드 갭을 형성시키는 연구 결과들이 보고된 바 있다. 그러나 이러한 방법들은 표면이 균일하지 않고, 그래핀에 많은 결함들이 발생한다는 단점이 있다. 이러한 단점을 극복하기 위해 자가조립 단층막(Self-assembled monolayers; SAMs)을 이용하여 이산화규소(Silicon oxide; SiO2) 기판을 기능화한 후 그 위에 그래핀을 전사하면 그래핀의 일함수를 쉽게 조절하여 소자의 전기적 특성을 최적화할 수 있다. SAMs는 그래핀과 SiO2 사이에 부착된 매우 얇고 안정적인 층으로 사용된 물질의 특성에 따라 운반자 농도나 도핑 유형, 디락 점(Dirac point)으로부터의 페르미 에너지 준위(Fermi energy level)를 조절할 수 있다[1-3]. 본 연구에서는 SAMs한 기판을 이용하여 그래핀의 도핑 효과를 확인하였다. CVD를 이용하여 균일한 그래핀을 합성하였고, 기판을 3-Aminopropyltriethoxysilane (APTES)와 Borane-Ammonia(Borazane)을 이용하여 각각 아민 기(Amine group; -NH2)와 보론 나이트라이드(Boron Nitride; BN)로 기능화한 후, 그 위에 합성한 그래핀을 전사하였다. 기판 위에 NH2와 BN이 SAMs 형태로 존재하는 것을 접촉각 측정(Contact angle measurement)을 통해 확인하였고, 그 결과 NH2와 BN에 의해 그래핀에 도핑 효과가 나타난 것을 라만 분광법(Raman spectroscopy)과 X-선 광전자 분광법(X-ray photoelectron spectroscopy: XPS)을 이용하여 확인하였다. 본 연구 결과는 안정적이면서 패턴이 가능하기 때문에 그래핀을 기반으로 하는 반도체 소자에 적용 가능할 것이라 예상된다.

• Applied Chemistry for Engineering
• /
• v.27 no.3
• /
• pp.313-318
• /
• 2016

In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.

• Korean Chemical Engineering Research
• /
• v.54 no.4
• /
• pp.574-581
• /
• 2016

In this study, CNT functionalized with pyrrolidine ring via 1,3-dipolar cycloaddition reaction with various amino acid and aldehyde was synthesized. Metallocene was subsequently immobilized on the functionalized CNT and CNT/polyethylene composite was prepared via in-situ ethylene polymerization. The polymerization activities of metallocene supported on CNT functionalized with glycine and benzaldehyde (Gly+BA-CNT) were similar to those of metallocene supported on CNT functionalized with N-benzyloxycarbonylglycine and paraformaldehyde (Z-Gly+PFA-CNT) although its Zr content was lower than that of Z-Gly+PFA-CNT. In the case of metallocene supported on Z-Gly+PFA-CNT, the even distribution of active sites hindered the diffusion of ethylene monomer and cocatalyst MAO due to steric hindrance during ethylene polymerization. Compared to polyethylene produced from homogeneous metallocene catalysts, CNT/PE composites had a higher initial degradation temperature ($T_{onset}$) and maximum mass loss temperature ($T_{max}$). It suggests that pyrrolidine functionalized CNT is uniformly dispersed and strongly interacted with the PE matrix, enhancing the thermal stability of PE.