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공간분할형 원자층증착 시스템을이용한리튬이차전지 분리막 코팅 연구
The conventional atomic layer deposition technique is the spatial method in which the deposition substrate is fixed precursors is injected over time, and an inert gas is injected to remove the precursor. The chemical reaction time for thin film deposition is determined by the chamber size and precursor exposure time. The conventional method has a rather long chemical reaction time so spatial atomic layer deposition technology has been developed. Spatial atomic layer deposition technology is a method of separating precursors according to space and can be applied to a roll-to-roll process which is advantageous for productivity and large-area production. In addition, it can be applied to polymers and flexible substrates through a low-temperature process so it can be introduced into secondary battery separators and flexible devices. In this thesis, based on a continuous process we developed a spatial atomic layer deposition head and system that can operate in low-temperature and atmospheric pressure environments and analyzed the characteristics of the thin film through process research. By coating the thin film(Al2O3 , Al2O3 -PVDF), the characteristics of the separator and the performance of the secondary battery were studied. The multi-slit atomic layer deposition head can deposit 400mm wide, and an external particle shielding module and head temperature control system have been developed to stabilize the process. We developed an optimized continuous process-based atomic layer deposition system such as precursor and transport gas control module for atomic layer deposition, head-substrate spacing and process temperature control module, roll-to-roll precision transport module, and system integration control UI. Based on this system, 10 nm of Al2O3 was coated on both sides of a separator (PE/PP/PE) at a low temperature of 90°C and analyzed using X-ray photoelectron spectroscopy, electrochemical impedance spectrum, and field emission scanning electron microscopy. The developed separator showed low thermal shrinkage and excellent wetting properties due to its high aspect ratio, conformal, step coverage, and uniform coating. The LiCoO2/Graphite battery manufactured with the developed separator showed a capacity retention rate of 79.5% after 100 charge/discharge cycles at 1C, and a discharge capacity of 140mAh/g was confirmed in a high temperature (80℃) environment. In addition, a study was conducted to improve thermal stability and mechanical strength by additionally coating PVDF with superior physical properties than existing separators. By depositing 5um PVDF and 10nm Al2O3 on both sides, electrolyte wettability was improved by 256% and shrinkage was minimized up to 180°C. It shows a fairly high discharge capacity of 130.9mAh/g at 0.5C after 150 charge/discharge cycles, and proves that it is a better solution, especially under high-temperature conditions, for high-capacity secondary batteries.
한국법을 준거법으로 한 선체용선계약의 법적 쟁점에 관한 비교법적 연구 -BARECON 양식을 중심으로- : -BARECON 양식을 중심으로-
이재욱 한국해양대학교 해사산업대학원 2020 국내석사
선체용선자는 선체용선계약을 통하여 선체용선기간 동안 선박소유자로부터 선박에 대한 전면적인 점유 및 지배․관리권을 넘겨받아 운용한다. 선체용선계약의 유형은 크게 운용형과 금융형 선체용선계약[예를 들면, 소유권취득조건부 선체용선계약(BBCHP)]으로 나누어 볼 수 있다. 운용형 선체용선계약은 BARECON 양식에 따라 체결되는 경우가 많다. BARECON은 선체용선계약 당사자가 계약에 적용될 준거법을 합의로 정할 수 있도록 하되, 별도의 합의가 없는 경우 영국법이 준거법이 된다고 규정한다. 한국법을 BARECON의 준거법으로 합의하는 경우, 운용형 선체용선계약은 그 법적성질이 임대차와 유사하므로 그 성질에 반하지 않는 이상 한국 민법의 임대차 규정이 준용된다. 선체용선계약은 당사자자치에 따라 규율되므로 한국 민법의 임의규정보다 BARECON 조항이 우선 적용되어 설령 임의규정과 일부 다른 내용이 있다고 하더라도 대부분의 조항에 있어서 그 해석과 법률효과에 있어서 영미법을 준거법으로 한 경우와 큰 차이는 없을 것이다. 그러나 한국 민법의 강행규정에 저촉되는 BARECON 조항은 효력이 없게 된다. 특히 민법 제627조와 제628조의 용선료 증감청구권은 강행규정으로 이에 반하여 선체용선자에게 불리한 조항은 효력이 없다. 따라서 비록 BARECON 2017 제3조 (c)항에서 선박이 용선자에게 인도된 이후에는 선박소유자의 의무는 전부 이행된 것으로 보고 그 이후에는 선체용선자가 법적 구제수단을 행사할 수 없다고 규정하고 있더라도, 선체용선자는 민법 제627조와 제628조를 근거로 용선료감액청구권을 행사할 수 있다. 선박소유자가 선박의 하자를 알면서 용선자에게 고지하지 아니한 경우에는 BARECON 2017 제3조 (c)항에도 불구하고, 민법 제584조에 따라 하자담보책임의 면제특약의 효력이 인정되지 않는다. BARECON 2017 제31조 (d)항의 도산해지조항에 따라 용선자가 도산한 경우 선박소유자는 선체용선계약을 해지하고 용선자의 영업자산인 선박에 대한 점유를 회복할 수 있다. 이 조항으로 인하여 용선자는 선박을 운용하여 이익을 얻을 수 없어 용선자의 회생이 곤란하게 되는 문제가 있다. 영국법을 준거법으로 하는 경우 도산해지조항의 효력이 인정될 가능성이 크다. 그러나 한국법을 준거법으로 한 경우 운용형 선체용선계약은 임대차의 성질을 가지므로 이를 쌍방미이행 쌍무계약으로 보아 관리인의 이행청구권을 보장하고 도산해지조항의 효력을 배제함으로써 도산절차에서의 안정성 및 용선자의 회생에 도움이 될 수 있다. 이처럼 BARECON 양식에 따른 운용형 선체용선계약을 체결하는 경우 준거법을 한국법으로 합의함으로써 도산절차에서의 안정성을 도모하고 경제사정의 변동에 따라 용선료증감청구를 할 수 있는 장점이 있다. 향후 많은 계약 당사자들이 BARECON 양식에 따른 운용형 선체용선계약의 준거법을 한국법으로 합의함으로써 이러한 장점을 활용할 수 있기를 기대한다. During the charter period the vessel shall be in full possession and at the absolute disposal for all purposes of the charterers and under their complete control in every respect. The bareboat charter can be classified into two large groups : Operating bareboat charter and Financing bareboat charter[for example, Bareboat Charter with Hire Purchase(BBCHP)]. It's very common for the parties to use the BARECON form for the operating bareboat charter. When the parties use the BARECON form, they can mutually agree the governing law and the arbitration place but they do not agree, the charter party shall be governed by and construed in accordance with English law. When the parties agree that the charter party shall be governed by and construed in accordance with Korean law, the provisions regarding leases under the Civil Act shall apply mutatis mutandis to the operating bareboat charter which is lease in nature according to Korean Law. Because the parties' intention shall prevail the optional provisions of Korean Civil Act, most of the articles of BARECON shall not be construed differently irrespective of governing laws, even though the articles are in contravention of the optional provisions of Korean Civil Act. But when some articles of BARECON are in contravention of the mandatory provisions of Korean Civil Act, the articles will be void. Especially, because the Article 627 and 628 of the Korean Civil Act are mandatory provisions, any articles of BARECON which are in contravention of the Article 627 and 628 and unfavorable to charterers shall be void. As a result, the charterers can demand a reduction of the hire on the ground of the Article 627 and 628 of the Korean Civil Act, even if BARECON 2017 article 3(c) says the delivery of the vessel by the owners and the taking over of the vessel by the charters shall constitute a full performance by the owners of all the owner's obligations under the clause, and thereafter the charterers shall not be entitled to make or assert any claim against the owners. The owners may not be relieved of liability in respect of any fact of which they were aware and nevertheless failed to disclose according to the Korean Civil Act article 584 in spite of BARECON 2017 Article 3(c). According to the Ipso Facto Clause[BARECON 2017 article 31(d)] when the charterers go bankrupt, the owners may terminate the charter party and repossess the vessel. Because of the clause, it is difficult for the charterers to make a profit by operating the vessel and to rehabilitate. When BARECON 2017 article 31(d) is governed by and construed in accordance with English law, the Ipso Facto Clause shall be in effect. But when the parties agree that article shall be governed by and construed in accordance with Korean law, the operating charter party which is lease in nature, shall be treated as the bilateral contract the parties have yet to complete performance of the contract, the custodian of the charterers has an option to terminate or require the owners to fulfill the owners' obligations. So the Ipso Facto Clause is not effective, it can help the charterer's rehabilitation. When the parties of the operating charter party agree that the charter party(BARECON form) shall be governed by and construed in accordance with Korean Law, it can help the rehabilitation of the charterers and the parties have the advantage of demanding the other party to raise or reduce the hire for the future when the economic situation changes. I wish that many parties agree the charter parties shall be governed by and construed in accordance with Korean Law and they can make good use of these advantages from now on.
The role of thymosin β-4 in vitro and in vivo based on primary cilia formation
Non-motile primary cilia are antenna-like organelles protruding from the cortical cell surface in most eukaryotic cells. And primary cilia is enriched with diverse signaling receptors and transduce signals from outside to inside. Since their diverse function and distribution, dysfunction of them results in severe developmental defects and organ homeostasis failure. Therefore, studying of primary cilia formation is important to understand pathological mechanisms of ciliopathies such as cancer and obesity. Thymosin beta-4 (Tβ4) is an actin-sequestering protein and involved in several cellular functions, such as cell migration, cell proliferation and tissue repair. Furthermore, it is over-expressed in highly invasive and aggressive cancer cells. When yeast two-hybrid screening was implemented by using Tβ4 as a bait, nephrocystin-3 (NPHP3), one of ciliary protein, was physically interacted. I examined effect of Tβ4 in vitro and in vivo on primary cilia formation and ciliopathies, especially cancer and metabolic disorders. For the first, I investigated whether Tβ4 regulates cilia formation by the association with NPHP3 in HeLa cervical cancer cells. I confirmed the direct binding of Tβ4 with NPHP3 by GST-pulldown assay and they were co-localized at the edge of cell peripheral surface. HeLa cells expressed noticeable number of primary cilia compared to that in many other cancer cells. Remarkably, inhibition of Tβ4 reduced primary cilia formation. Also, the ciliated cell number increased in Tβ4-GFP positive cells. The number of ciliated cells was reduced by the inhibition of NPHP3. In addition, the frequency of primary cilia in NPHP3-overexpressed cells was reduced by knockdown of Tβ4. In the point of molecular correlation, NPHP3 was decreased by the inhibition of Tβ4, but it was increased by Tβ4 overexpression. In contrast, Tβ4 expression was not affected by neither the interference nor overexpression of NPHP3. Taken together, the results demonstrate that primary cilium formation could be affected by Tβ4 through the regulation of NPHP3. It suggests that tumorigenesis could be associated with the perversion in Tβ4 and/or NPHP3 expression to maintain primary cilia formation normally. Reactive oxygen species (ROS) are continuously generated during metabolic process and involved in cellular signaling and homeostasis. The production of ROS is also stimulated by cellular stress, such as growth factor deprivation. Serum starvation increased total ROS level in HeLa cells. And the frequency of ciliated cells were decreased by ROS scavenger, NAC, under the serum starve condition. We examined whether ROS are associated in Tβ4-mediated primary cilia formation. Inhibition of Tβ4 reduced ROS generation whereas Tβ4 expression was not affected by serum deprivation. Also, Hydrogen peroxide (H2O2), the one of ROS, increased in serum starvation. Treatment of H2O2 increased ciliated cell number that was attenuated by catalase, the H2O2 degrading enzyme. Moreover, the serum starvation-increased H2O2 was declined by knockdown of Tβ4. The H2O2–induced ciliogenesis was also reduced by knockdown of Tβ4. These results suggest that Tβ4 could affect ciliogenesis through the generation of ROS. Based on the findings that primary cilia could be increased by Tβ4 in cancer cells, I investigated whether Tβ4-induced primary cilia leads malignant phenotypes in cancer cells. Vinblastine, an anti-tumor drug,-induced cell death decreased in serum staved HeLa cells. In contrast, Inhibition of primary cilia by ciliobrevin A (cilioA) increased vinblastine-induced cell death. Furthermore, Tβ4-overexpression reduced anti-tumor activity of vinblastine and the drug resistance was lessened by inhibition of primary cilia. These findings suggest Tβ4 could lead resistance to vinblastine via induction of primary cilia. Type2 diabetes mellitus (T2DM) is caused by genetics and/or environmental factors such as eating high-fat foods. Tβ4 has an anti-fibrotic and anti-inflammatory effect on several T2DM complications. In addition, it regulated ciliogenesis. And primary cilia is involved in regulation of energy balance and metabolic process. I investigated the effects of Tβ4 on High fat diet (HFD)-induced obesity and T2DM with the association of primary cilia in vivo. Weight increase by HFD was significantly reduced in Tβ4-transgenic mouse group compared to C57BL6 control group although food consumption was even higher in Tβ4 group. Adipose tissue amounts and adipocytes size was considerably reduced in Tβ4 group. Lower level of plasma leptin was also showed in Tβ4 group. In addition, fatty liver was noticeably inhibited in Tβ4 group. Furthermore, Tβ4 group improved glucose control and insulin sensitivity with the prevention of hyperinsulinemia. Therefore, data demonstrated Tβ4 prevented HFD-induced lipogenesis and obesity and improved glucose and insulin intolerance. Next, to see the effect of primary cilia on metabolic disorder, I treated cilioA to dampen cilia number in mouse. Weight gain, fatty liver and glucose regulation was not affected by cilioA in HFD-WT group. The lipid accumulation in adipose tissue rather slightly decreased. Nevertheless, the fasting insulin level was worsen by cilioA. Since the number of primary cilia was well maintained in HFD-Tβ4-Tg mouse compared to that in HFD-WT mouse, when the maintained primary cilia was inhibited by cilioA in HFD-Tβ4-Tg mouse, glucose intolerance and insulin sensitivity was aggravated. Taken together, Tβ4 might have anti-diabetic properties correlated with maintaining primary cilia in obese state. It suggests that Tβ4 likely be a novel restrainer of morbid obesity and T2DM caused by bad eating habits. Collectively, Tβ4 may regulate primary cilia formation through the control of NPHP3 or ROS production in HeLa cervical cancer cells. Cancer cells with primary cilia may acquire the malignant properties by showing resistance to vinblastine anticancer drugs. In addition, the expression of Tβ4 in the metabolic disorder showed the improvement effect of obesity and diabetes mellitus, which could be seen as the effect of in vivo energy and metabolism control through maintenance of primary cilia.