Nano-ZnO/Laponite/PVA 광촉매 흡착볼의 메틸렌블루 제거효율 평가

오주현(Ju Hyun Oh),안호상(Ho Sang Ahn),장대규(Dae Gyu Jang),안창혁(Chang Hyuk Ahn),이새로미(Sae Romi Lee),주진철(Jin Chul Joo) 大韓環境工學會 2013 대한환경공학회지 Vol.35 No.9

광촉매인 나노크기의 산화아연(ZnO)과 흡착기능의 지지체인 Laponite, 결합제인 poly vinyl alcohol (PVA)를 혼합하여 붕산(boric acid)과 가교반응(crosslinking)을 통해 흡착과 광분해가 동시에 발생하며 회수가 불필요한 nano-ZnO/Laponite/PVA(ZLP) 광촉매 흡착볼을 개발하였다. ZLP 광촉매 흡착볼 제작을 위한 최적의 배합비는 Nano-ZnO:Laponite:PVA:deionized water의 구성비가 3:1:1:16 (by weight)으로 도출되었으며, PVA가 붕산과의 가교결합을 통해서 다층의 망(mesh network)과 막(film)을 형성하여 Laponite의 팽윤과 ZnO의 탈리 현상을 억제하는 것으로 사료된다. 수중안정성을 개선하고 비표면적을 높이기 위한 최적의 건조방법은 microwave를 활용하는 방법이며, SEM과 TEM의 분석을 통해 다양한 크기(55~500μm)의 공극(pore)이 분포하며 ZnO의 균질한 분포를 확인할 수가 있었다. 메틸렌블루 광분해 특성은 반응 초기(40분)에는 Laponite와 메틸렌블루의 이온결합에 따른 흡착제거가 주요 제거 기작이며, 메틸렌블루의 흡착이 포화상태에 도달 후 광분해를 통한 제거가 발생함을 확인하여 흡착과 광분해가 동시에 발생하여 수중에 용해된 메틸렌 블루를 효과적으로 제거할 수 있음을 확인하였다. 본 연구를 통해 짧은 시간에 흡착과 광분해가 동시에 진행되어 난분해성 오염물질을 효과적으로 제거하는 광촉매 흡착볼의 제작이 가능하며, 나노물질의 탈리로 인해 발생하는 환경 및 수용체에 미치는 위해성도 최소화 할 수 있을 것으로 판단된다. In order to overcome drawbacks (i.e., filtration and recovery) of conventional powder type photocatalysts, nano- ZnO/Laponite/PVA (ZLP) photocatalyzed adsorption balls were developed by using in situ mixing of nanoscale ZnO as a photocatalyst, and Laponite as both adsorbent and supporting media in deionized water, followed by the poly vinyl alcohol polymerization with boric acid. The optimum mixing ratio of nano-ZnO:Laponite:PVA:deionized water was found to be 3:1:1:16 (by weight), and the mesh and film produced by PVA polymerization with boric acid might inhibit both swelling of Laponite and detachment of nanoscale ZnO from ZLP balls. Drying ZLP balls with microwave (600 watt) was found to produce ZLP balls with stable structure in water, and various sizes (55~500 μm) of pore were found to be distributed based on SEM and TEM results. In the initial period of reaction (i. e., 40 min), adsorption through ionic interaction between methylene blue and Laponite was the main removal mechanism. After the saturation of methylene blue to available adsorption sites for Laponite, the photocatalytic degradation of methylene blue occurred. The effective removal of methylene blue was attributed to adsorption and photocatalytic degradation. Based on the results from this study, synthesized ZLP photocatalyzed adsorption balls were expected to remove recalcitrant organic compounds effectively through both adsorption and photocatalytic degradation, and the risks of environmental receptors caused by detachment of nanoscale photocatalysts can be reduced.

조미김 포장을 위한 PET/PVA-BA/OPP 다층필름 제조 및 특성분석

임미진,김도완,서종철,Lim, Mijin,Kim, Dowan,Seo, Jongchul 한국포장학회 2017 한국포장학회지 Vol.23 No.1

수증기 및 산소에 대한 차단성이 개선된 PVA-BA 코팅 조성액의 포장소재로의 적용가능성을 확인하기 위하여 콤마 코팅과 라미네이션 공정을 이용하여 PET/PVA-BA/OPP 다층필름을 제조하였다. PCT 전 후의 PET/PVA-BA/OPP 다층필름의 기체, 수증기 차단특성 및 인장강도를 확인하였고 이를 PA/PA/EVOH/PP 다층필름의 물성과 비교하였다. PVA내 BA 함량이 증가함에 따라 물성이 증가하는 것을 확인할 수 있었지만, PCT 후 PET/PVA-BA/OPP 다층필름의 산소, 수증기 차단특성 및 인장강도는 감소하는 경향을 보였다. 이는 PVA-BA층 내 증가한 가교밀도와 관련이 있는 것으로 판단된다. 또한, 조미김을 이용한 저장특성분석에서, PET/PVA-BA/OPP다층필름은 PP/Al-metallized PP 다층필름에 비해 조미김의 지방산화를 야기시키는 요인을 효과적으로 억제하는 것으로 판단된다. 하지만, PP/Al-metallized PP 다층필름에 비해 PET/PVA-BA/OPP 다층필름의 상대적으로 높은 수분투과특성 때문에 Aw에 큰 장점을 확인하지 못하였다. 따라서, 물성 극대화 및 포장소재로 적용을 위해서는 PET/PVA-BA/OPP 다층필름 내 수분 차단성 향상에 대한 추가적인 연구가 필요하다는 것을 확인하였다. To identify applicability for packaging material of polyvinyl alcohol (PVA)/boric acid (BA) coating solution with highly-enhanced water vapor and oxygen barrier properties, the PET/PVA-BA/OPP multi-layer films were prepared through comma coating and lamination process. The oxygen and water vapor permeabilities, and tensile strength of as-prepared multi-layer films were investigated before and after pressure cooker test (PCT). Although oxygen and water vapor permeabilites, and mechanical properties of PET/PVA-BA/OPP multi-layer films was decreased after PCT, their properties were highly enhanced as increase of BA contents in PVA matrix. This is strongly related with enhanced cross-linking density in PVA-BA layer. In storage test of seasoned-laver, the PET/PVA-BA/OPP multi-layer films were comparatively effective to suppress the increase in peroxide value originating from oxidation of seasoned-laver. Comparing the commercially available PP/Al-metallized PP for seasoned-laver packaging, however, PET/PVA-BA/OPP multi-layer films did not show any advantage in water activity. This is due to higher water vapor permeation properties of as-prepared multi-layer films. Therefore, further studies are required to enhance the water vapor permeation in PET/PVA-BA/OPP multi-layer films.

Enhanced oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) blended with poly(acrylic acid) for packaging applications

Lim, Mijin,Kim, Dowan,Seo, Jongchul John Wiley Sons, Ltd 2016 Polymer international Vol.65 No.4

<P><B>Abstract</B></P><P>To enhance the oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) (PVA) and expand its food packaging applicability, five crosslinked poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend films were prepared via esterification reactions between hydroxyl groups in PVA and carboxylic acid groups in PAA. The physical characteristics of the blends, including the thermal, barrier, mechanical and optical properties, were investigated as a function of PAA ratio. With increasing PAA content, the crosslinking density was significantly increased, resulting in changes in the chemical structure, morphology and crystallinity of the films. The oxygen transmission rate of pure PVA decreased from 5.91 to 1.59 cc m<SUP>−1</SUP> day<SUP>−1</SUP> with increasing PAA ratio. The water resistance, too, increased remarkably. All the blend films showed good optical transparency. The physical properties of the blend films were strongly correlated with the chemical structure and morphology changes, which varied with the PAA content. © 2016 Society of Chemical Industry</P>

Preparation and Properties of Poly(vinyl alcohol)/Vinyltrimethoxysilane (PVA/VTMS) Hybrid Films with Enhanced Thermal Stability and Oxygen Barrier Properties

임미진,서종철,김도완,한학수 한국고분자학회 2014 Macromolecular Research Vol.22 No.10

To enhance the thermal stability and barrier properties of pure poly(vinyl alcohol) (PVA), a series ofpoly(vinyl alcohol)/vinyltrimethoxysilane (PVA/VTMS) hybrid films were prepared via a sol-gel process, and theirphysical properties were investigated as a function of VTMS content. During the sol-gel process, simultaneous reactionsbetween hydroxyl groups of PVA and silanol groups of hydrolyzed VTMS and self-condensation of VTMSoccurred, inducing a cross-linked network structure and greatly enhanced thermal stability and oxygen barrier properties. The glass transition temperature and thermal decomposition temperature (T5%) of the PVA/VTMS hybridfilms increased from 72.6 to 84.3 oC and 273.6 to 342.2 oC, respectively, with increasing VTMS content from 0 to20%. Oxygen transmission rates of the hybrid films decreased from 6.12 to 0.17 cm3/m2×day, and those of the hybridfilms incorporating 5%, 10%, and 20% VTMS were suppressed by 65.7%, 95.6%, and 97.2%, respectively, versusa pure PVA film. These are dependent on the chemical structure and morphology of the films with differing initialamounts of VTMS. The chemical affinity for water, intermolecular packing, and rigidity in polymer chains increasedwith increasing cross-linking by VTMS, leading to enhanced oxygen barrier properties and thermal stability in thePVA/VTMS hybrid films.

직접 메탄올 연료전지 적용을 위한 PVA 기반 양이온교환막 제조 및 특성연구

전이슬,김가영,임지원 한국막학회 2015 멤브레인 Vol.25 No.2

수용성 고분자인 poly(vinyl alcohol) (PVA)에 가교제인 sulfosuccinic acid (SSA)를 첨가하여 가교반응을 통해 물에 용해되지 않는 막을 제조하였으며, 이온교환능력을 부여하기 위해 poly(4-styrene sulfonic acid-co-maleic acid) (PSSA_MA)를 PVA 질량대비 70, 80, 90 wt%로 달리 첨가하여 막을 제조하였다. 제조한 막의 특성을 알아보기 위해 FT-IR, 함수율, 이온교환용량, 이온전도도, 메탄올 투과도를 측정하였다. 함수율과 이온교환용량, 이온전도도는 PSSA_MA 함량이 증가할수록 증가하는 경향을 나타내었으며 메탄올 투과도는 감소하는 경향을 나타내었다. 특성평가 결과 본 실험 막의 최적 조성은 PVA10/SSA9/ PSSA_MA80으로 도출되었다 The water-soluble poly(vinyl alcohol) membranes with the addition of sulfosuccinic acid (SSA) were prepared and to assign the ion exchange capacity, poly(4-styrene sulfonic acid-co-maleic acid) (PSSA_MA) was added to PVA according to PSSA_MA contents of 70, 80 and 90 wt%. To characterize the resulting membranes, FT-IR, water contents, ion exchange capacity, proton conductivity and methanol permeability were measured. As PSSA_MA contents increased, water contents, ion exchange capacity, proton conductivity increased, but methanol permeability decreased. From these results, the best preparation component was known as PVA10/SSA9/PSSA_MA80.

Preparation and Characterization of Regenerated Cellulose Blend Films Containing High Amount of Poly(vinyl alcohol) (PVA) in Ionic Liquid

Xiaomin Zhang,Jin Zhu,Xiaoqing Liu 한국고분자학회 2012 Macromolecular Research Vol.20 No.7

Regenerated cellulose/poly(vinyl alcohol) (PVA) blend films in ionic liquid 1-allyl-3-methylimidazolium chloride (AMIMCl) were successfully prepared by coagulating with water. The structures and properties were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). SEM images indicated that there was good compatibility between cellulose and PVA. The XRD results showed that the crystallinity of cellulose was significantly decreased from 42.8% up to 29.4% with increasing PVA content. The blend film with a 10 wt% PVA demonstrated the best mechanical performance. Its tensile strength and modulus showed 97 and 5,100 MPa, respectively compared with 69 and 3,400 MPa of neat cellulose film. The elongation also increased 50%. In addition, the transparency of the blend lms was still maintained well, and the shrinkage of the regenerated cellulose film was greatly improved with incorporation of PVA. The possible mechanism of forming cellulose/PVA blend films was proposed in the process of regeneration and dissolution.

직접 메탄올 연료전지 적용을 위한 PVA 기반 양이온교환막 제조 및 특성연구

전이슬,김가영,임지원,Jeon, Yi Seul,Kim, Ka young,Rhim, Ji Won 한국막학회 2015 멤브레인 Vol.25 No.2

수용성 고분자인 poly(vinyl alcohol) (PVA)에 가교제인 sulfosuccinic acid (SSA)를 첨가하여 가교반응을 통해 물에 용해되지 않는 막을 제조하였으며, 이온교환능력을 부여하기 위해 poly(4-styrene sulfonic acid-co-maleic acid) (PSSA_MA)를 PVA 질량대비 70, 80, 90 wt%로 달리 첨가하여 막을 제조하였다. 제조한 막의 특성을 알아보기 위해 FT-IR, 함수율, 이온교환용량, 이온전도도, 메탄올 투과도를 측정하였다. 함수율과 이온교환용량, 이온전도도는 PSSA_MA 함량이 증가할수록 증가하는 경향을 나타내었으며 메탄올 투과도는 감소하는 경향을 나타내었다. 특성평가 결과 본 실험 막의 최적 조성은 PVA10/SSA9/PSSA_MA80으로 도출되었다. The water-soluble poly(vinyl alcohol) membranes with the addition of sulfosuccinic acid (SSA) were prepared and to assign the ion exchange capacity, poly(4-styrene sulfonic acid-co-maleic acid) (PSSA_MA) was added to PVA according to PSSA_MA contents of 70, 80 and 90 wt%. To characterize the resulting membranes, FT-IR, water contents, ion exchange capacity, proton conductivity and methanol permeability were measured. As PSSA_MA contents increased, water contents, ion exchange capacity, proton conductivity increased, but methanol permeability decreased. From these results, the best preparation component was known as PVA10/SSA9/PSSA_MA80.

Preparation and Release Properties of Electrospun Poly(vinyl alcohol)/ Poly(ε-caprolactone) Hybrid Nanofibers: Optimization of Process Parameters via D-Optimal Design Method

Payam Zahedi,Iraj Rezaeian,Seyed Hassan Jafari,Zeinab Karami 한국고분자학회 2013 Macromolecular Research Vol.21 No.6

The main purpose of this work was to develop biomedical electrospun nanofibrous mats based on a poly(vinyl alcohol)/poly(ε-caprolactone) (80/20) hybrid with a defined drug release rate using tetracycline hydrochloride as a model drug. The electrospinning process parameters, such as polymer solution concentration, distance between injecting syringe tip/collector, voltage, injected flow rate and the polyvinyl alcohol crosslinking time were optimized via a D-optimal design method for a suitable nanofiber diameter with an optimal drug release rate. The morphology of nanofibers and their mean diameters were studied by a scanning electron microscopy technique. The results showed that the mean diameters of nanofibers were significantly reduced after drug loading. The swelling,weight loss and biodegradability of nanofibers samples investigated by FTIR were also determined. Two main mechanisms via penetration and erosion were evaluated. In vitro drug release in a phosphate buffer environment at pH=7.2for the samples demonstrated that the polymer type and hydrophilic nature of the polymer/drug system is very effective in the kinetics and mechanism of drug release. Hybridization of poly(vinyl alcohol)/poly(ε-caprolactone) with a known ratio showed to be a suitable and useful method in the electrospinning of nanofibers samples for superior control of the drug release rate. Finally, nanofibrous mats of polyvinyl alcohol and polyvinyl alcohol/poly(ε-caprolactone)hybrid (80/20) had much better drug release rate characteristics for tetracycline hydrochloride as a model drug compared with cast film samples loaded with the same drug.

STA-PVAm polyelectrolyte complex surface deposited PVA membrane for dehydration of Epichlorohydrin, isopropanol, and water ternary feed mixtures

( Chaudhari Shivshankar Subhash ),손민영,남승은,박유인 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.1

In this study Poly (vinyl alcohol) (PVA)-tetraethyl orthosilicate organicinorganic hybrid membrane has prepared and modified the membrane surface by layer-by-layer deposition of a PVAm/silicotungstic acid polyelectrolyte for the pervaporation dehydration of ECH/IPA/water mixtures. Membrane characterization using FTIR, FE-SEM, and SEMEDS, XPS and TGA measurements was carried out. In pervaporation experiments at 30 °C, the flux decreased 0.14 to 0.05 kg m-2 h-1 and separation factor increased from and 2099 to 13320 with TEOS addition in the PVA membrane was observed. And for the layer by layer deposition on PVA-TEOS (4) membranes flux increased and separation factor decreased from 0.14 to 0.28 kg m-2 h and 2099 to 416 with the number of layer of deposition were observed. The pervaporation output of the PVA-TEOS and layer by layer PVA-TEOS membranes reflects the both membranes have excellent ability in epichlorohydrin, isopropanol and water ternary mixture pervaporation dehydration.

알로인이 함유된 창상치료제용 PVA/CMC 하이드로젤의 개발

김진(Jin Kim),이창문(Chang Moon Lee),김동운(Dong Woon Kim),이기영(Ki Young Lee) 한국고분자학회 2013 폴리머 Vol.37 No.6

알로인이 첨가된 하이드로젤을 제조하여 창상치유의 효과를 관찰하였다. Poly(vinyl alcohol)(PVA)과 carboxyl methyl cellulose(CMC)를 동결-융해 방법으로 결합시킨 하이드로젤을 제조하였다. 젤의 특성과 약물의 방출, in vivo 창상치유 실험 및 병리학적 평가를 진행하였다. 쥐 등에 만든 상처의 치유 실험은 알로인이 첨가된 PVA/CMC(5:5)하이드로젤 그룹과 대조군 그룹의 알로인이 함유된 카보머934 젤 혹은 순수 카보머934 젤로 처치한 그룹보다 CMC 의 수분과 알로인의 피토케미칼 활성 때문에 빠른 치유력을 확인할 수 있었다. 결론적으로 알로인이 첨가된 창상용드레싱으로 5% PVA, 5% CMC 그리고 0.125% 알로인의 조성은 상처치료에 효과적이며 창상용 드레싱으로 활용을기대할 수 있다. The purpose of this study was to develop an aloin-loaded wound dressing with an enhanced healing effect. The cross-linked hydrogel films were prepared with poly(vinyl alcohol) (PVA) and carboxyl methyl cellulose (CMC) using a freeze-thawing (F-T) method. Their gel properties, release of drug, in vivo wound healing effect and histopathology were then evaluated. In the wound healing test, this aloin loaded PVA/CMC hydrogel showed faster healing of the wound made in rat dorsum than the aloin carbomer 934 gel or the control (carbomer 934 gel) due to phytochemical activity of aloin and moisture of CMC. In conclusion, the aloin-loaded wound dressing composed of 5% PVA, 5% CMC and 0.125% aloin is a potential wound dressing with enhanced wound healing effect.