Journal Search Engine
Search Advanced Search Adode Reader(link)
Download PDF Export Citaion korean bibliography PMC previewer
ISSN : 1226-0088(Print)
ISSN : 2288-7253(Online)
Membrane Journal Vol.29 No.2 pp.105-110
DOI : https://doi.org/10.14579/MEMBRANE_JOURNAL.2019.29.2.105

Fabrication of Micro-Porous Membrane via a Solution Spreading Phase Inversion Method

Ook Choi*, Chul Ho Park**
*Research Institute of Basic Sciences, Incheon National University, 119 Academy-ro, Yeonsu-gu, Incheon 22012, Korea
**Jeju Global Research Cesnter (JGRC), Korea Institute of Energy Research (KIER), 200, Haemajihaean-ro, Gujwa-eup, Jeju Specific Self-Governing Province 63357, South Korea
Corresponding author(e-mail: chpark@kier.re.kr)
March 19, 2019 April 18, 2019 April 29, 2019

Abstract


Porous membranes are widely used in industry for removing particulate matter. Unlike conventional porous membrane fabrication methods, the solution spreading phase separation method can form pores very simply. The first step is to wet the mesh with the support layer, then to let the polysulfone solution flow into a solvent without water. The solvent is readily vaporized and the polysulfone is made into a thin film. When the polysulfone solution is mixed with water to form pores, the pore size can be adjusted according to the concentration ratio of the polysulfone solution. The thickness of the membrane is easily controlled by the concentration of the solution. The porous separator has the formation of meshes intact and is very useful for forming a three-dimensional structure. The solution spreading phase separation method proposed in this study is characterized by its high cost competitiveness compared with conventional membranes due to its low production cost and easy process control.



용액 퍼짐 상분리법을 통한 마이크로 기공 분리막 제조

최 욱*, 박 철 호**
*인천대학교 기초과학연구소
**한국에너지기술연구원 제주글로벌연구센터

초록


다공성 분리막은 입자성 물질을 제거하는데 산업적으로 다양하게 응용되고 있다. 기존 다공성 분리막 제작 방법 과 다르게, 용액퍼짐 상분리법은 매우 간단하게 기공을 형성할 수 있다. 먼저 지지층으로 메쉬 위에 물을 적신 후, 물과 혼합 되지 않은 용매에 폴리설폰 용액을 흘려준다. 이때 물과 혼합되지 않은 용매는 쉽게 기화되어 폴리설폰은 얇은 막으로 만들 어지게 된다. 기공을 형성하기 위해 폴리설폰 용액에 물과 혼합할 수 있는 물질을 넣게 되면, 넣어주는 농도 비율에 따라 기 공크기를 조절할 수 있게 된다. 막의 두께는 쉽게 용액의 농도로 조절이 된다. 다공성 분리막은 메쉬의 형성을 그대로 유지하 고 있어 3차원 구조체를 형성하는데 매우 유용하다. 본 연구에서 제시된 용액 퍼짐 상분리법은 매우 낮은 생산단가와 쉬운 공정조절에 의해 기존 분리막에 비해 높은 가격경쟁력을 가질 수 있는 특징을 보이고 있다.



1. Introduction

Over the last two decades, membrane filtration products - microfiltration (MF) and ultrafiltration (UF) - have proliferated globally to remove suspended solids, colloids, pathogens and emulsions[1-3]. Unlike conventional methods such as gravity based flotation and clarification, MF and UF method do not require chemical coagulation because the effective desired pore size could be controlled[4].

UF and MF membranes have been typically synthesized by phase inversion method due to cost effect mass production[5]. If the target materials could be dissolved in organic solvents, the pore is simply formed as mixing the poor solvents. This method is named as non-solvent induced phase inversion (NIPS). In case of some polymers such as polyethylene or polypropylene, it would be difficult to find proper organic solvent to dissolve them at room temperature. At this time, those polymers could be dissolved in diluents at high temperatures. Based on the thermodynamic, the phase separation takes place when the temperature is cooled until binomial points. This method is called as thermally induces phase separation (TIPS)[6,7]. Current commercialized MF and UF membranes are released using TIPS or NIPS. However, since both methods have been well known relatively, the technical barrier is relatively low. A novel technique to achieve a competitive price must be developed with well controllable pore size[8].

As one approach, the amount of used materials must be minimized. The volume portion of solvents or diluents for NIPS and TIPS is around 80%[9-12]. They occupy around 50% in the production cost except for incidental expenses. Even though those solvent or diluent could be recyclable, those are wasted in most cases. Also, it takes at least 1 week to remove remained solvents and diluents or use pore-forming chemical agents such as glycerin. In addition, the coagulation liquids are also the additional cost. The additional process could also increase the production cost.

This study introduces a novel method, named as a solution spreading phase inversion method, which produces a porous membrane in several seconds without any additional next process. The solution spreading is based on the solvent spreading on water. The solvent spreading must stratify two conditions; 1) the solvent should be buoyant in the subphase (water) without sinking and dissolving, 2) the solvent must spread on the surface of water. The solvent spreading is easily observed when the polymeric solutions were dropped on water. However, the film is typically not uniform because of the uncontrollable combination phenomenon among gravity, surface tension, evaporation, or shrinkage, etc. To put the handing condition, the suitable solvent is primary searched. However, it would be difficult to find the suitable solvent with relatively cost-effective solvent removal and Hansen solubility parameter matching. More important things, the film must have pore structures to show the ability of membrane. However, until recently, there is no study about a solution spreading phase inversion method to fabricate the membrane. Therefore, this study exhibits that the suggested method is very unique to fabricate the MF membrane with satisfying all the needs.

2. Experimental

As the model polymer, polysulfone (PSf) was purchased from BASF (Germany). The solvent, N,N-dimethyformaide (DMF), dichloromethane (DCM), and chloroform (CF) were purchased from Duck San Pure Chem. (Korea). As pore-forming agents, dimethylsulfoxide (DMSO) and blenched polyethyleneimine (PEI) were purchased from Sigma-Aldrich (USA). The polyester mesh (350 mesh) was used as the support layer. The images of samples were obtained using an optical microscopy (OM; Olympus, Japan), and a mini-SEM (COXEM, Korea) after Pt coating. The flux of water was measured using a home-made coupon cell (effective area: 18 cm2) with distilled water.

The mesh was deposited on the glass. The water was filled in the all area to occupy all the holes. After PSf solutions was spread on the mesh as Fig. 1. The mesh was transferred into a convection oven at 60°C for 5 minutes to remove water.

3. Results and Discussion

PSf polymer has the Hansen solubility parameter of 21.2 MPa1/2. DMF (24.9 MPa1/2), DCM (20.2 MPa1/2) and CF (19.0 MPa1/2) as the proper solvent to dissolve PSf were selected. Three solvents are used to spread on water (not shown data). The solution spreading ability was simply observed as one solution was very gently dropped on water. When the mesh filled by water was used, the spreading phenomena were different. When the DMF solution was dropped on water-filled mesh, the solution disappeared and did not show clearly spreading. Unlike free subphase water, the mesh could influence an additional effect during the solution spreading because of physical interactions between solution and mesh. However, although PSf solutions with DMF could be spread on the mesh, PSf film did not be fabricated as shown in Fig. 2(a).

When DCM and CF were used for PSf solutions, the solution spreading was observed. The boiling points of DCM and CF were 39.6 and 61.2°C, respectively. The evaporation kinetic depends on the environmental conditions (e.g., temperature, wind, and viscosity) but spreading thickness is around several millimeter (which is approximately calculated by the thickness of PSf films) [13,14]. Therefore, the spreading solution was visually solidified under several seconds.

The fast evaporation rate could influence complicated solidification and phase separation mechanism. Under high humidity conditions, the fast evaporation could condense water droplet on the polymer solution that Breath-Fig. structure could take place. However, OM images show that CF solution (Fig. 2(c)) seem to have porous structure compared to DCM (Fig. 2(b)). The relative humidity in laboratory was around 62%. Also, the liquid water was filled in the mesh. Thus, this porous structure could not result from the water condensation.

To understand the pore formation mechanism, one hypothesis is suggested; if an additive is miscible and dissolve with PSf as well as water, it could act as the water absorbent during evaporation and solidification. If the additives could absorb the water molecules, the phase separation could occur and form the pores such as a non-solvent phase separation mechanism[15]. To prove this assumption, PEI was chosen.

Figs. 3 and 4 exhibit OM and SEM images at various PEI concentrations. When PEI was not added into PSf solutions, pores of PSf films cannot be observed. However, the pore is formed when PEI was added into PSf solutions. The result might provide that the assumption could be reasonable. Furthermore, the pore size could be facilely controlled by only concentration of water-soluble contents without complicated operating factors (e.g., temperature, humidity, or flow rate, etc.) and long-term solvent exchange time in the case of a non-solvent exchange membrane[16].

To confirm our assumption, a water-soluble solvent, DMSO, was used. As shown in Fig. 5, the pore is formed like PEI. The pore size also increases with increasing in the concentration of DMSO. There are various water soluble organic solvents in the range of PSf’s Hensen solubility parameter. Although this study did not show the results using the other organic solvents effects, tetrahydrofuran, DMF, and 1-methyl-2-pyrrolidinone could also form the pore similar to DMSO trends. Although the pore characterization had not been systematically examined, OM and SEM images provide the possibility about controlling the pore size.

Fig. 6 shows the cross-section images. Without PEI addition, the PSf (Fig. 6(a)) film has the thickness of below 1 μm. When PEI was added within PSf solutions, the thickness is around 2 μm because the addition of PEI corresponds to increase of concentration. The thickness of porous PSf film increases with increasing solution concentrations. Thus, the film thickness could be relatively simply controlled by the concentration of polymer solutions.

The flux is a critical important factor to characterize the porous membrane. The PSf film without PEI does not show any water flux. However, when PEI is added, the flux (Fig. 7) increases with increasing in the concentration similar to Fig. 4. Thus, the flux as well as pore size is closely related to the concentration of PEI. At the same composition ratio (1 : 1 w/w) between PSf and PEI, the flux does not have dominant dependence on the thickness in the error range (not shown data).

The solution spreading phase inversion method is unique to control the pore size as well as thickness. This method could hold a great potential with respect to economic feasibility; no additional post-treatment, very fast fabrication process, and reasonable reproducibility without high-cost environment control process. More interesting advantage is that this method can fabricate the three-dimensional structure as Fig. 8 in which the mesh provides the three-dimensional architecture. The density of DCM is heavier than water so the film could compress the water. Thus, the level of PSf solutions at the hole of meshes is lower than that of the mesh surface. Thus, the PSf film was solidified on the curvature of the interface and surface zone. The level dependent results in the three dimensional structure of PSf films. Due to no chemical adhesion force between PSf film and mesh, the porous PSf film can be easily detached. After that, the porous PSf film has the original structure of mesh. Although this study used only mesh, any type of supports could be used to design the architecture.

4. Conclusion

This study focused on the fabrication of porous polysulfone membrane using the solution spreading phase inversion method. As the immiscible organic solvent was used for the solution spreading on water, the film could be easily formed. The pore size can be controlled by the concentration of water-miscible matters in organic solution. The thickness of porous PSf films is controlled by the total solution concentration. The spreading methods are interesting to fabricate three-dimensional architecture. Although this study could not show more detailed fabrication mechanism as well as characterization, this method could hold intensive potentials with respect to economic feasibility as well as novel membrane designs.

Acknowledgements

This work was conducted under the Research and Development Program of the Korea Institute of Energy Research (KIER) (B9-244-01).

Figure

MEMBRANE_JOURNAL-29-2-105_F1.gif

Schematic illustration of a solution spreading method to prepare porous polysulfone membrane.

MEMBRANE_JOURNAL-29-2-105_F2.gif

Optical microscopy images of PSf (5 wt%) membranes with (a) DMF, (b) DCM, (c) CF prepared on water- filled mesh via a solution spreading method. The scale bar respond to 25 μm.

MEMBRANE_JOURNAL-29-2-105_F3.gif

Optical microscopy images of PSf (DCM, 5 wt%) membranes with (a) 0 wt% PEI, (b) 1 wt%, (c) 2 wt%, (d) 3 wt%, (e) 4 wt%, (f) 5 wt% prepared on water-filled mesh via a solution spreading method. The scale bar respond to 50 μm.

MEMBRANE_JOURNAL-29-2-105_F4.gif

SEM images of PSf (DCM, 5 wt%) membranes with (a) 0 wt% PEI, (b) 1 wt%, (c) 2 wt%, (d) 3 wt%, (e) 4 wt%, and (f) 5 wt% prepared on water-filled mesh via a solution spreading method. The scale bar respond to 3 μm.

MEMBRANE_JOURNAL-29-2-105_F5.gif

Optical microscopy images of PSf (DCM, 5 wt%) membranes with (a) 15 : 1 (b) 15 : 2, (c) 15 : 3 DCM/ DMSO v/v. The scale bar respond to 25 μm.

MEMBRANE_JOURNAL-29-2-105_F6.gif

SEM Images of PSf film; (a) 1 wt% PSf, (b) 1 wt% PSf and 1 wt% PEI, (b), 2 wt% and 2 wt%, (c) 3 wt% and 3 wt%, (d) 4 wt% and 4 wt%, (e) 5 wt% and 5 wt%, and (f) 6 wt% and 6 wt%. The solvent was DCM. The scale bar responds to 10 μm.

MEMBRANE_JOURNAL-29-2-105_F7.gif

Water flux of PSf membrane as a function of PEI concentration. The concentration of PSf is 5 wt%.

MEMBRANE_JOURNAL-29-2-105_F8.gif

Porous PSf membrane after being detached from the mesh. The scale bar responds to 100 μm.

Table

Reference

  1. L. R. Fukumoto, P. Delaquis, and B. Girard, “Microfiltration and ultrafiltration ceramic membranes for apple juice clarification”, J. Food Sci., 65, 1 (1998).
  2. B. J. Wang, T. C. Wei, and Z. R. Yu, “Effect of operating temperature on component distribution of West Indian cherry juice in a microfiltration system”, LWT - Food Sci. Technol., 35, 683 (2005).
  3. B. Razi, A. Aroujalian, and M. Fathizadeh, “Modeling of fouling layer deposition in cross-flow microfiltration during tomato juice clarification”, Food Bioprod. Process., 90, 841 (2012).
  4. J. Caro, “Basic principles of membrane technology”, Zeitschrift Für Phys. Chemie., 203, 1 (2011).
  5. M. Sadrzadeh and S. Bhattacharjee, “Rational design of phase inversion membranes by tailoring thermodynamics and kinetics of casting solution using polymer additives”, J. Memb. Sci., 441, 31 (2013) doi: 10.1016/j.memsci.2013.04.009.
  6. J. R. Werber, C. O. Osuji, and M. Elimelech, “Materials for next-generation desalination and water purification membranes”, Nat. Rev. Mater., 1, 16018 (2016) doi:10.1038/natrevmats.2016.18.
  7. A. L. Zydney, Membrane handbook edited by W. S. Winston Ho, and Kamalesh K. Sirkar, “Van nostrand reinhold”, New York, 1992, 954 pp. 131.95, AIChE J., 41, 954 (2004).
  8. B. Wang, J. Ji, C. Chen, and K. Li, “Porous membranes prepared by a combined crystallisation and diffusion (CCD) method: Study on formation mechanisms”, J. Memb. Sci., 548, 136 (2018).
  9. W. Choi, P. G. Ingole, J. S. Park, D. W. Lee, J. H. Kim, and H. K. Lee, “H2/CO mixture gas separation using composite hollow fiber membranes prepared by interfacial polymerization method”, Chem. Eng. Res. Des., 102, 297 (2015).
  10. W. Choi, P. G. Ingole, H. Li, S. Y. Park, J. H. Kim, H. K. Lee, and I. H. Baek, “Facilitated transport hollow fiber membrane prepared by t-Bu CoSalen for O2/N2 separation”, Microchem. J., 132, 36 (2017).
  11. S. ichi Sawada, C. Ursino, F. Galiano, S. Simone, E. Drioli, and A. Figoli, “Effect of citrate-based non-toxic solvents on poly(vinylidene fluoride) membrane preparation via thermally induced phase separation”, J. Memb. Sci., 493, 232 (2015).
  12. J. T. Jung, J. F. Kim, H. H. Wang, E. di Nicolo, E. Drioli, and Y. M. Lee, “Understanding the non-solvent induced phase separation (NIPS) effect during the fabrication of microporous PVDF membranes via thermally induced phase separation (TIPS)”, J. Memb. Sci., 514, 250 (2016).
  13. D. Mackay and C. D. McAuliffe, “Fate of hydrocarbons discharged at sea”, Oil Chem. Pollut., 5, 1 (1989).
  14. M. L. Spaulding, “A state-of-the-art review of oil spill trajectory and fate modeling”, Oil Chem. Pollut., 4, 39 (1988).
  15. H. Bin Li, W. Y. Shi, Y. F. Zhang, D. Q. Liu, and X. F. Liu, “Effects of additives on the morphology and performance of PPTA/PVDF in situ blend UF membrane”, Polymers., 6, 1846 (2014).
  16. M.-T. Lee, W.-C. Hung, F.-Y. Chen, and H. W. Huang, “Mechanism and kinetics of pore formation in membranes by water-soluble amphipathic peptides”, Acta Crystallogr. Sect. A Found. Crystallogr., 64, 5087 (2015).