skip to main content


Title: Layer‐by‐layer approach to enable polyamide formation on microporous supports for thin‐film composite membranes
Abstract

Polyamide thin‐film composite (PA‐TFC) membranes make large‐scale desalination effective. Interfacial polymerization (IP) is used to make PA‐TFC membranes, but it may limit the range of monomers that can be used, which hinders progress toward advanced membranes. Layer‐by‐layer (LbL) sequential deposition could circumvent kinetic and thermodynamic limitations of the conventional IP process to facilitate incorporation of different co‐monomers into the membrane. The selective layer needs to be deposited onto a microporous support, but depositing LbL coatings on microporous supports often results in defective membranes. Using a poly(vinyl alcohol) (PVA) primer between the support and the LbL polyamide layer may prevent defect formation. The water permeance and salt rejection of a three layer, PVA‐primed, LbL‐based PA‐TFC membrane are discussed and compared to a membrane made without the PVA primer and a commercially available membrane. Mass transfer resistances are analyzed using a series resistance model and appear to be small or even negligible compared to that of the polyamide layer. Incorporation of a sulfonated co‐monomer into the polyamide via LbL is reported. The combination of a PVA primer layer and LbL sequential deposition may expand the range of co‐monomers that could be used relative to polyamide membranes prepared by the conventional IP process.

 
more » « less
Award ID(s):
2001624
NSF-PAR ID:
10450159
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Journal of Applied Polymer Science
Volume:
138
Issue:
41
ISSN:
0021-8995
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. This study revealed the effects of incorporating ionic liquid (IL) molecules: 1-ethyl, 1-butyl, and 1-octyl-3-methyl-imidazolium chlorides with different alkyl chain lengths, in interfacial polymerization (IP) on the structure and property (i.e., permeate-flux and salt rejection ratio) relationships of resulting RO membranes. The IL additive was added in the aqueous meta-phenylene diamine (MPD; 0.1% w/v) phase, which was subsequently reacted with trimesoyl chloride (TMC; 0.004% w/v) in the hexane phase to produce polyamide (PA) barrier layer. The structure of resulting free-standing PA thin films was characterized by grazing incidence wide-angle X-rays scattering (GIWAXS), which results were correlated with the performance of thin-film composite RO membranes having PA barrier layers prepared under the same IP conditions. Additionally, the membrane surface properties were characterized by zeta potential and water contact angle measurements. It was found that the membrane prepared by the longer chain IL molecule generally showed lower salt rejection ratio and higher permeation flux, possibly due to the inclusion of IL molecules in the PA scaffold. This hypothesis was supported by the GIWAXS results, where a self-assembled surfactant-like structure formed by IL with the longest aliphatic chain length was detected. 
    more » « less
  2. Abstract

    Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Achieving such a precise separation using membranes requires Angstrom scale pores with a high level of pore size uniformity. Herein, we demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization (SARIP). The dynamic, self-assembled network of surfactants facilitates faster and more homogeneous diffusion of amine monomers across the water/hexane interface during interfacial polymerization, thereby forming a polyamide active layer with more uniform sub-nanometre pores compared to those formed via conventional interfacial polymerization. The polyamide membrane formed by SARIP exhibits highly size-dependent sieving of solutes, yielding a step-wise transition from low rejection to near-perfect rejection over a solute size range smaller than half Angstrom. SARIP represents an approach for the scalable fabrication of ultra-selective membranes with uniform nanopores for precise separation of ions and small solutes.

     
    more » « less
  3. Abstract

    Nanoparticle (NP) additions can substantially improve the performance of reverse osmosis and nanofiltration polyamide (PA) membranes. However, the relative impacts of leading additives are poorly understood. In this study, we compare the effects ofTiO2andSiO2NPs as nanofillers in PA membranes with respect to permeate flux and the rejection of organic matter (OM) and salts. Thin‐film nanocomposite (TFN) PA membranes were fabricated using similarly sizedTiO215 nm andSiO2(10 – 20 nm)NPs, introduced at four different NP concentrations (0.01, 0.05, 0.2, and 0.5% w/v). Compared with PA membranes fabricated without NPs, membranes fabricated with nanofillers improved membranes hydrophilicity, membrane porosity, and consequently the permeability. Permeability was increased by 24 and 58% with the addition ofTiO2andSiO2, respectively. Rejection performance and fouling behavior of the membranes were examined with salt (MgSO4andNaCl) and OM (humic acid [HA] and tannic acid [TA]). The addition ofTiO2andSiO2nanofillers to the PA membranes improved the permeability of these membranes and also increased the rejection ofMgSO4, especially for TiO2membranes. The addition ofTiO2andSiO2to the membranes exhibited a higher flux and lower flux decline ratio than the control membrane in OM solution filtration. TFN membranes' HA and TA rejections were at least 77 and 71%, respectively. The surface change properties of NPs appear to play a dominant role in determining their effects as nanofillers in the composite membrane matrix through a balance of changes produced in membrane pore size and membrane hydrophilicity.

     
    more » « less
  4. Abstract

    Controlled growth of crosslinked polyamide (PA) thin films is demonstrated at the interface of a monomer‐soaked hydrogel and an organic solution of the complementary monomer. Termed gel–liquid interfacial polymerization (GLIP), the resulting PA films are measured to be chemically and mechanically analogous to the active layer in thin film composite (TFC) membranes. PA thin films are prepared using the GLIP process on both a morphologically homogeneous hydrogel prepared from poly(2‐hydroxyethylmethacrylate) and a phase‐separated, heterogeneous hydrogel prepared from poly(acrylamide). Two monomer systems are examined: trimesoyl chloride (TMC) reacting with m‐phenylene diamine (MPD) and TMC reacting with piperazine (PIP). Unlike the self‐limiting growth behavior in TFC membrane fabrication, diffusion‐limited, continuous growth of the PA films is observed, where both the thickness and roughness of the PA layers increase with reaction time. A key morphological difference is found between the two monomer systems using the GLIP process; TMC/MPD produces a ridge‐and‐valley surface morphology whereas TMC/PIP produces nodule/granular structures. The GLIP process represents a unique opportunity to not only explore the pore characteristics (size, spacing, and continuity) on the resulting structure and morphology of the interfacially polymerized thin films, but also a method to modify the surface of (or encapsulate) hydrogels.

     
    more » « less
  5. Abstract

    Ovarian cancer is especially deadly, challenging to treat, and has proven refractory to known immunotherapies. Cytokine therapy is an attractive strategy to drive a proinflammatory immune response in immunologically cold tumors such as many high grade ovarian cancers; however, this strategy has been limited in the past due to severe toxicity. We previously demonstrated the use of a layer‐by‐layer (LbL) nanoparticle (NP) delivery vehicle in subcutaneous flank tumors to reduce the toxicity of interleukin‐12 (IL‐12) therapy upon intratumoral injection. However, ovarian cancer cannot be treated by local injection as it presents as dispersed metastases. Herein, we demonstrate the use of systemically delivered LbL NPs using a cancer cell membrane‐binding outer layer to effectively target and engage the adaptive immune system as a treatment in multiple orthotopic ovarian tumor models, including immunologically cold tumors. IL‐12 therapy from systemically delivered LbL NPs shows reduced severe toxicity and maintained anti‐tumor efficacy compared to carrier‐free IL‐12 or layer‐free liposomal NPs leading to a 30% complete survival rate.

     
    more » « less