scholarly journals Asymmetric block copolymer membrane fabrication mechanism through self-assembly and non-solvent induced phase separation (SNIPS) process

2022 ◽  
Vol 12 (1) ◽  
Author(s):  
Afshin Hamta ◽  
Farzin Zokaee Ashtiani ◽  
Mohammad Karimi ◽  
Sareh Moayedfard

AbstractIn this paper, the concept of the functional mechanism of copolymer membrane formation is explained and analyzed from the theoretical and experimental points of view. To understand the phase inversion process and control the final membrane morphology, styrene-acrylonitrile copolymer (SAN) membrane morphology through the self-assembly phenomena is investigated. Since the analysis of the membrane morphology requires the study of both thermodynamic and kinetic parameters, the effect of different membrane formation conditions is investigated experimentally; In order to perceive the formation mechanism of the extraordinary structure membrane, a thermodynamic hypothesis is also developed based on the hydrophilic coil migration to the membrane surface. This hypothesis is analyzed according to Hansen Solubility Parameters and proved using EDX, SAXS, and contact angle analysis of SAN25. Moreover, the SAN30 membrane is fabricated under different operating conditions to evaluate the possibility of morphological prediction based on the developed hypothesis.

Materials ◽  
2019 ◽  
Vol 12 (12) ◽  
pp. 1890 ◽  
Author(s):  
Yang Yu ◽  
Ning Chu ◽  
Qiaode Pan ◽  
Miaomiao Zhou ◽  
Sheng Qiao ◽  
...  

A series of organogelators based on L-phenylalanine has been synthesized and their gelation properties in various organic solvents were investigated. The results showed that these organogelators were capable of forming stable thermal and reversible organogels in various organic solvents at low concentrations, and the critical gel concentration (CGC) of certain solvents was less than 1.0 wt%. Afterward, the corresponding enthalpies (ΔHg) were extracted by using the van ’t Hoff equation, as the gel–sol temperature (TGS) was the function of the gelator concentration. The study of gelling behaviors suggested that L-phenylalanine dihydrazide derivatives were excellent gelators in solvents, especially BOC–Phe–OdHz (compound 4). The effects of the solvent on the self-assembly of gelators were analyzed by the Kamlet–Taft model, and the gelation ability of compound 4 in a certain organic solvent was described by Hansen solubility parameters and a Teas plot. Morphological investigation proved that the L-phenylalanine dihydrazide derivatives could assemble themselves into an ordered structure such as a fiber or sheet. Fourier-transform infrared spectroscopy (FTIR) and hydrogen nuclear magnetic resonance (1H NMR) studies indicated that hydrogen bonding, π–π stacking, and van der Waals forces played important roles in the formation of a gel.


2013 ◽  
Vol 9 ◽  
pp. 1826-1836 ◽  
Author(s):  
Valeria C Edelsztein ◽  
Andrea S Mac Cormack ◽  
Matías Ciarlantini ◽  
Pablo H Di Chenna

Supramolecular gels are an important and interesting class of soft materials that show great potential for many applications. Most of them have been discovered serendipitously, and understanding the supramolecular self-assembly that leads to the formation of the gel superstructure is the key to the directed design of new organogels. We report herein the organogelating property of four stereoisomers of the simple steroid 2,3-dihydroxycholestane. Only the isomer with the trans-diaxial hydroxy groups had the ability to gelate a broad variety of liquids and, thus, to be a super-organogelator for hydrocarbons. The scope of solvent gelation was analysed with regard to two solvent parameters, namely the Kamlet–Taft and the Hansen solubility parameters. The best correlation was observed with the Hansen approach that revealed the existence of two clear gelation zones. We propose a general model of self-assembly through multiple intermolecular hydrogen bonds between the 1,2-dihydroxy system, which is based on experimental data and computational simulations revealing the importance of the di-axial orientation of the hydroxy groups for the one-dimensional self-assembly. Under controlled conditions, the fibrillar superstructure of the organogel was successfully used as a template for the in-situ sol–gel polymerization of tetraethoxysilane and the further preparation of silica nanotubes. We propose that the driving forces for templating are hydrogen bonding and electrostatic interactions between the anionic silicate intermediate species and the self-assembled fibrillar network.


Membranes ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 418
Author(s):  
Muhammad Azam Rasool ◽  
Ivo F. J. Vankelecom

γ-Valerolactone (GVL) was selected as a renewable green solvent to prepare membranes via the process of phase inversion. Water and ethanol were screened as sustainable non-solvents to prepare membranes for nanofiltration (NF). Scanning electron microscopy was applied to check the membrane morphology, while aqueous rose Bengal (RB) and magnesium sulphate (MgSO4) feed solutions were used to screen performance. Cellulose acetate (CA), polyimide (PI), cellulose triacetate (CTA), polyethersulfone (PES) and polysulfone (PSU) membranes were fine-tuned as materials for preparation of NF-membranes, either by selecting a suitable non-solvent for phase inversion or by increasing the polymer concentration in the casting solution. The best membranes were prepared with CTA in GVL using water as non-solvent: with increasing CTA concentration (10 wt% to 17.5 wt%) in the casting solution, permeance decreased from 15.9 to 5.5 L/m2·h·bar while RB rejection remained higher than 94%. The polymer solubilities in GVL were rationalized using Hansen solubility parameters, while membrane performances and morphologies were linked to viscosity measurements and cloudpoint determination of the casting solutions to better understand the kinetic and thermodynamic aspects of the phase inversion process.


2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>


Membranes ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 461
Author(s):  
Fu Yang ◽  
Zhengkun Huang ◽  
Jun Huang ◽  
Chongde Wu ◽  
Rongqing Zhou ◽  
...  

Ultrafiltration is a promising, environment-friendly alternative to the current physicochemical-based tannery wastewater treatment. In this work, ultrafiltration was employed to treat the tanning wastewater as an upstream process of the Zero Liquid Discharge (ZLD) system in the leather industry. The filtration efficiency and fouling behaviors were analyzed to assess the impact of membrane material and operating conditions (shear rate on the membrane surface and transmembrane pressure). The models of resistance-in-series, fouling propensity, and pore blocking were used to provide a comprehensive analysis of such a process. The results show that the process efficiency is strongly dependent on the operating conditions, while the membranes of either PES or PVDF showed similar filtration performance and fouling behavior. Reversible resistance was the main obstacle for such process. Cake formation was the main pore blocking mechanism during such process, which was independent on the operating conditions and membrane materials. The increase in shear rate significantly increased the steady-state permeation flux, thus, the filtration efficiency was improved, which resulted from both the reduction in reversible resistance and the slow-down of fouling layer accumulate rate. This is the first time that the fouling behaviors of tanning wastewater ultrafiltration were comprehensively evaluated, thus providing crucial guidance for further scientific investigation and industrial application.


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