서지주요정보
Surface wettability control of porous membrane via vapor phase deposition process = 기상 증착 공정을 이용한 다공성 멤브레인의 표면 젖음성 조절
서명 / 저자 Surface wettability control of porous membrane via vapor phase deposition process = 기상 증착 공정을 이용한 다공성 멤브레인의 표면 젖음성 조절 / Youngmin Yoo.
발행사항 [대전 : 한국과학기술원, 2016].
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8029800

소장위치/청구기호

학술문화관(문화관)B1층 보존서고

DCBE 16034

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A membrane is selective barrier that some materials can penetrate through the pores and other materials can be blocked. Recently, for the efficient separation, many researches for assigning various functionality have been received great attention. In the whole study of this thesis, the novel vapor deposition method called iCVD process (initiated chemical vapor deposition) is introduced for simply and efficiently modifying wettability of porous substrates like membranes. Owing to the advantages of vapor phase deposition, delicate substrate easily damaged by solvents can be modified. Also, the polymer film can be conformally deposited on the pattern or porous substrate. Using this iCVD process, firstly, robust superhydrophobic polymer was deposited on porous substrate. This polymer film shows superhydrophobicity as well as good chemical and mechanical stability. Second, surface energy-controlled membrane was fabricated for separating microalgal lipids from wet biomass. Third, the Janus property was assigned which has both hydrophobicity and hydrophilicity. Simple etching process was applied to superhydrophobic polymer coated porous substrate. At last, the hydrophilic and underwater oleophobic polymer was deposited on porous membrane for efficient oil/water separation including oil/water emulsion.

분리막은 선택적으로 한 물질은 통과하고 다른 물질은 막아주는 역할을 한다. 최근 효율적인 분리를 위해 분리막 표면에 다양한 기능성 그룹을 부여하는 연구가 많이 진행되었다. 본 학위논문에서는 새로운 기상 증착 공정인 iCVD공정을 이용하여 쉽고 효율적으로 다공성 분리막의 표면을 개질 하여 표면 젖음성을 조절하였다. 기상 증착이라는 장점으로 인해 손상되기 쉬운 기판에도 증착 가능하고 다공성 기판에도 얇고 균일한 코팅을 가능케 하였다. 이런 기상 증착 공정을 이용해 먼저 고분자 박막을 적층하여 다공성 기판에 내구성 있는 초발수 코팅을 적용하였다. 이와 함께 만들어진 초발수 코팅을 분리막에 적용하여 물과 미세조류로부터 추출한 기름을 분리하는 연구를 진행하였다. 또한 초발수 코팅이 된 기판의 반대면에 간단한 에칭과정을 적용하여 친수성을 부여하는 연구를 진행하였다. 이렇게 다양한 기능성 고분자들을 기상 증착 공정을 통해 증착하여 다공성 구조를 가지는 여러 분리막의 표면 젖음성을 조절하였다.

서지기타정보

서지기타정보
청구기호 {DCBE 16034
형태사항 xiii, 107 p. : 삽화 ; 30 cm
언어 영어
일반주기 저자명의 한글표기 : 유영민
지도교수의 영문표기 : Sung Gap Im
지도교수의 한글표기 : 임성갑
학위논문 학위논문(박사) - 한국과학기술원 : 생명화학공학과,
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Schematic images ofvarious coating methods (a) Dipcoating (b) Spin coating (C) Spray coating(d) Layer-by-layerassembly (e) CVD process

Schematic image of surface modified membrane

Schematic image and advantages ofiCVD process

A schematic structure of stacked polymer coated fabric. The stacked polymeris composed ofp(V4D4) and p(PFDA).

(a) Cross sectional SEM image ofp(V4D4-L-PFDA) stacked polymer film on Si wafer. Top layer is p(PFDA) layer, middle layer is p(V4D4) layer, and bottom layer is Si wafer (b) Digital camera images of p(PFDA)-coated Si wafer (left) and p(V4D4-L-PFDA) stacked polymer-coated Si wafer (right) after a thermal treatment at 120 OC for 24hrs. Each inset is the enlarged optical microscopy image of each sampl

(a), (b), (c) SEM images of non-coated polyester fabric surface, slightly rough p(V4D4-L-PFDA) stacked polymer-coated fabric surface, rougher surface of p(V4D4-L- PFDA) stacked polymer coated fabric, respectively. Inset images show the hysteresis between a water droplet and fabric. (d), (e), (f) represent AFM images of Si wafer obtained from the same experimentbatch as the fabrics shown in (a), (b

(a) SEM images of a pristine (left) and a p(V4D4-L-PFDA) stacked polymer- coated polyester fabric (right). (b) Transmittance of 700 nm-thick p(V4D4-L-PFDA) stacked polymer coated PET film. Both groups of inset images of (a) and (b) are digital camera images which show that the substrate maintains the same feature and color but displays superhydophobicity afterp(V4D4-L-PFDA) stacked polymercoating.

Contact angle changes after the chemical and mechanical stresses. (a) Contact anglechanges afterthe thermal test at 120 'C and -16'C. (b) Contactangle changes with UV irradiation and ultrasonication test (c) Contact angle changes with various solvents test (Acetone, IPA, Ethanol, THF, and Toluene). (d) Hysteresis graph of p(V4D4-L-PFDA)· coated polyesterfabric before and afterthermal, sonication,

(a) Water contact angles plotted with respectto the number oflaundry cycles (b) SEM image of stacked polymerfilm coated polyesterfabric surface. (c) SEM image offabric surface afterlaundry test. (d) SEM image of fabric surface after abrasion test. Inset images show the shapes of waterdroplets on the each fabric surface.

A schematic image of entrapped air pocketbetween the coated fabric and water droplet.

(a) SEM image of p(V4D4-L-PFDA) stacked polymer-coated fabric. (b) EDS elemental mapping of fluorine on the same fabric. (c) Merged image of SEM and EDS elemental mappingimages.

(a), (b), (c) Contact angle images of p(V4D4-L-PFDA) coated-polyester fabric after soaking in H2SO4 (pH 2), KOH (pH 12), and H2O2fora period of24hrs, respectively. (d), (e) SEM images ffp(V4D4-L-PFDA) polyesterfabric after soaking in H2SO4 (pH2) and KOH (pH 12), respectively.

Schematic illustration of overall iCVD process forthe surface modification ofthe SUS membrane (top) and the separation ofFFME-in-chloroform by the fabricated membrane (bottom). The OM image on the bottom right demonstrates the surface of the pPFDMA- coated SUS membrane.

(a) FT-IR spectra of PFDMA monomer (top) and the corresponding pPFDMA polymer (bottom) with the representative vinyl group (gray region) and perfluoroalkyl group (blue region) peaks. (b) SEM images with X 5000 (left), X 200 (middle), and X 800 (right) times magnification, respectively, ofbare (top) and pPFDMA-coated SUS membrane (bottom

Wettability analysis: 10ul droplets of water/MeOH (5:1 v/v, dyed in dark blue) and chloroform (dyed in red) (a) on bare and pPFDMA-coated SUS plate and (b) on bare and pPFDMA-coated SUS membrane. (c) The measured contact angle values of water and DIM on the SUS plate, calculated surface free energy of bare and pPFDMA-coated SUS membrane, and the corresponding interfacial energies with the contact

(a) Digital camera images of membrane separation of liquid mixture of water/Me0H and olive oil-in-chloroform. (b) Measured fluxes of olive oil-in-chloroform through the pPFDMA-coated SUS membrane from olive oil-in-chloroform only and water/MeOH-olive oil-in-chloroform mixture. (c) Photograph showing that the pPFDMA- coated SUS membrane with the contact area of 11.3 cm2 can resist the gravity force

(a) Experimental setup of microalgal biomass separation by the surface energy controlled membrane from the mixture of water/MeOH and FAME-in-chloroform (5:1:: volumeratio). (b) OM imageofhomogeneous mixed water/MeOH and FAME-in-chloroforr (top,left) and the filtered FAME-in-chloroform in the permeate phase (bottom, left), and th photographs of pPFDMA-coated SUS membrane before (top, right) and aft

Water contact angle values ofiCVD polymer-coated SUS membrane before and after the exposure to water, MeOH, and chloroform at 25 iC for 15hr.

Surface free energy components of liquids, water, DIM, chloroform, and water/MeOH (5/1, volume ratio)

(a) Schematic procedure of the fabrication process of porous Janus substrate: After coating the porous substrate conformally with PHFDMA usingiCVD, the substrate was floated on top of KOH (aq) solution to hydrolyze the ester bond in the polymer and convert only one side of the PHFDMA-coated substrate hydrophilic (b) Reaction scheme for hydrolysis; after polymerization, the ester group (circled in

(a) The minimum required exposure time forpolyesterJanus fabric to reach WCA < 30이 is plotted as a function of temperature of 1 M KOH (aq) solution. As shown, as temperature increases, the time required for hydrolysis decreases exponentially. (b) Contact angle values ofpolyesterJanus fabric exposed to 1 M KOH (aq) solution at25 'C plotted asa function of exposure time. While the contact angle valu

Images of water droplets on the Janus-faced surfaces with different substrates: (a) polyester fabric (b) nylon mesh (c) filter paper, respectively. The contact angle values of PHFDMA-coated substrate and top side ofJanus substrate is very similar to each other while that ofthe bottom side is significantly decreased. (d) The contact angle data for bare substrate, and top and bottom sides ofJanus su

Still-shot images of polyesterJanus fabric: (a) Janus fabric is placed on top of water and chloroform (dyed with Oil Red 0) (b) The syringe is vigorously shaken to induce mixing (c)Janus fabric is placed in the interface between water and chloroform.

Functionalized Janus nylon mesh: (a), (b) Optical microscope and fluorescence images of hydrophilic side of Janus mesh functionalized with fluorescent PS particles, respectively. (c), (d) Optical microscope and fluorescence images of hydrophobic side of Janus mesh, respectively (scale bar = 100 nm). The appearance offunctionalized nylon mesh is similar to that of non-functionalized mesh except the

Cross-sectional SEM image of Nylon coated with PHFDMA using iCVD. As shown in this figure, a 15-minute depositionyielded a 250-nm thick PHFDMA film.

SEM images of polyester fabric before (left) and after (right) coating with PHFDMA using iCVD. As shown, the surface morphology ofthe fabric remains unchanged, which allows watervaporand air molecules to easily pass through.

Digital camera image ofJanus fabric (left) indicating the static contact angle at edge(right, top) and atthe center(right, bottom)

A schematic image of pHVDS-coated PE separator. The HVDS monomer was polymerized by an iCVD process to conformally deposit cross-linked polymer, pHVDS, on the PE separator.

SEM images of PE separators in (a) low and (b) high magnifications after different deposition times. (c) FT-IR and XPS spectra (leftinset) of the pristine PE separator (black) and pHVDS-coated PE separator (red). The right insetimageis an enlarged view of FT-IR spectra in the region of 750~1500 cm-1. (v-stretching; 6-bending; 0-wagging; T- twisting; a-asymmetric; s-symmetric).

(a) Thermal shrinkage and (b) SEM images of the pristine PE (left), pHVDS- 20min PE (middle), and pHVDS-40min PE (right) after storage at 140 C for 30 min. (c) Areal shrinkage of each separator.

Water contact angles of (a) the pristine PE and (b) pHVDS-40min PE. The electrolyte wettability tests of(c) the pristine separatorand (d) pHVDS-40min PE. The tips of both separators were contacted with the electrolyte att=0. The pictures were taken att=2h.

Electrochemical characterization for the cells with and without the pHVDS coating on PE separators. (a) Voltage profiles of the cells with the pristine and pHVDS- coated PE during the first cycle at0.1C (1C=150 mA g-1) in the voltage range of2.4~4.2V. (b) Rate performance tests for all the cells at different C-rates from 1C to 15C. (c) Nyquist plots for all the cells measured after the 70 cycles s

(a,b) SEM images of the pristine PE (left), pHVDS-20min PE (middle), and pHVDS-40min PE (right) after the 70 cycles shown in Figure 5-5b at(a) low (x5000) and(b high (x 20000) magnifications. (c) FT-IR and XPS spectra (inset) of pHVDS-40min PE before and afterthesame 70 cycles.

Basic physical properties of the pristine PE, pHVDS-20min PE, and pHVDS- 40min PE.

(a) The overall thickness and (b) the average pore size variation of the pristine PE, pHVDS-20min PE, and pHVDS-40min PE.

A cross-sectional SEM image of pHVDS-40min PE (top left) along with the EDS elemental mappings with respect.oo carbon, silicon, and oxygen.

(a) Thermal shrinkage of pHVDS-50min PE after incubating at 140 C for 30 min and (b) the SEM imageof pHVDS-50min PE before the incubation.

Remained area and electrolyte uptake amount plots as a function of pHVDS deposition time. pHVDS-40min PE was selected as a main sample for comprehensive electrochemical testing.

(a) DSC curves of the pristine and pHVDS-coated PE. The inset image 1S an enlarged view in the region of 120~160 C. The DSC analysis clearly shows that the melting point of the pHVDS-coated PE is higher than that of the pristine PE. (b) DSC curve of pHVDS polymer in the temperature range of 25~1000 C. All of the DSC measurements -1 were conducted at a heating rate of10 C min under N2 atmosphere.

(a) Thermal shrinkage tests for the PE separators coated based on different processes after incubation at 140 C for 30 min. (b) The loading weights after the three coating processes shown in (a).

(a) The electrolyte uptake and (b) the ionic conductivity results of the pristine and pHVDS-coated PE separators at various coating time. The uptake tests were conducted with fixed soakingtime (200s).

An SEM image of pHVDS polymer coated on the SS plate.

Voltage profiles of the cells with the pristine and pHVDS-coated PE at different current densities during the rate tests shown in Figure 5-5b.

Nyquist plots for all the cells measured before cycling. (Inset) The same Nyquistplots zoomed in around the origin.

(a) Rate performance tests forthe cells using the pristine and pHVDS-coated PE at different current densities. (b) Nyquist plots for the same cells measured after the 70 cycles shown in Figure 5-5b. To present the pHVDS-50min PE data (green) clearly, other colors are dimmed out.

Nyquist plots for the pristine (black) and pHVDS-40min (red) cells measured aftera heattreatmentat140 C for30 min.

Higherresolution SEM images (X 160000). Pristine PE separator and pHVDS- 40min PE separatorbefore and after70 cycles.

Overall scheme of the thesis

Schematicimage of pHEMA photopolymerization on SUS mesh

(a) The water contact angle (WCA) of bare membrane, pHEMA coated membrane and oil contactangle (OCA) of pHEMA coated membrane. (b) The digital camera images of waterdropleton pHEMA coated mesh (left) and after 1s (right).

Separation of water (bottom) and hexane (top) mixture by usingpHEMA coated mesh

Separation of water/ethanol (bottom) and hexane/olive oil (top) mixture by using pHEMA coated mesh