Contrôle de la porosité dans les films SiOCH de polymère-plasma pour la séparation gazeuse

La synthèse d'une membrane composite formée d'une couche fine de surface de structure très réticulée et permsélective aux gaz déposée sur un substrat poreux a été étudiée comme solution pour accroître la perméabilité aux gaz tout en conservant une sélectivité importante. Une couche mince de polymère-plasma SiOCH a été retenue comme membrane de séparation gazeuse car elle possède une structure dont l'ultramicroporisté peut être contrôlée en ajustant les paramètres du procédé plasma comme la puissance, le flux de monomère et la pression de travail. Néanmoins, dans la membrane SiOCH, la taille moyenne des pores et leur distribution sont difficiles à appréhender par des techniques de caractérisation classiques, notamment proche de la surface car elle est très fine. Ce mémoire de thèse concerne le contrôle de la structure poreuse dans une couche mince de polymère-plasma SiOCH déposée sur un substrat polymère en utilisant un précurseur organosilicié. La spectroscopie d'annihilation de positron couplée à un faisceau de positron lent a été utilisée pour identifier la microstructure de couches minces SiOCH avec la profondeur. Ceci a nécessité tout d'abord l'acquisition d'une bonne connaissance de la caractérisation de l'annihilation de positron de matériaux polymères et céramiques. Des couches minces de SiOCH conformes ou superhydrophobes (SHP) ont été obtenues à deux fréquences différentes, respectivement à 13,56 MHz ou 40 kHz. Pour une couche conforme, le type de substrat, la structure chimique du précurseur et la puissance RF sont les paramètres majeurs qui influencent la structure des pores. Quand les films de SiOCH sont composées de deux couches (couche uniforme de surface et couche de transition) déposées sur un substrat poreux, l'analyse PAS met en évidence une couche de transition large et l'ensemble possède une perméabilité aux gaz élevée grâce à la porosité de surface du support. Lors de la préparation des couches minces SHP, quand la pression totale dépasse 0,6 mbar, la nucléation en phase gaz apparaît ce qui augmente la rugosité de la surface. Ceci induit des angles de contact à l'eau supérieurs à 160 et une hystérésis d'angles de contact avancée-reculée de seulement 2. La préservation des chaînes carbonées et la microstructure sont les facteurs déterminant pour accroître l'hydrophobicité des couches minces de SiOCH.In gas separation, the fabrication of composite membranes consisting of a permselective thin top layer with high cross-linking structures and a porous substrate has been regarded as a solution for improving gas permeability and simultaneously retaining high selectivity. A plasma-polymerized SiOCH film has been known as an appropriate gas separation membrane because it possesses a dense structure, the crosslinking degree of which could be controlled by adjusting plasma parameters such as plasma power, monomer flow rate, and system pressure. However, the pore size and distribution in SiOCH films, especially in the region of depth profile, are difficult to measure by conventional techniques because of they are very thin.This thesis is concerned with the control of pore structure in a plasma-polymerized SiOCH film on a polymeric substrate by using an organosilicon source. The positron annihilation spectroscopy (PAS) coupled to the slow positron beam technique was used to identify the microstructure of SiOCH films as a function of depth. This step required to have a good understanding of the positron annihilation characteristics of different materials such as organic, inorganic, and hybrid materials. Depending on plasma frequency adjustments, SiOCH films with a flat and a superhydrophobic (SHP) surface were fabricated at 13.56 MHz and 40 kHz, respectively. For a flat SiOCH film, substrate type, chemical structure of precursor, and RF power were the major variables that influenced the pore structure. When SiOCH films composed of two layers (bulk and transitions layers) were deposited on porous substrates, they displayed a long transition layer based on the PAS analysis and possessed a high gas permeability due to the surface porosity of the substrate. When the precursor used possessed a cyclic ring structure, an opportunity of a break-up of the cyclic ring would increase with increasing RF power and then induce formation of new big pores. For the preparation of SHP films, when the total pressure was higher than 0.6 mbar, the gas nucleation reaction was enhanced to induce roughness on SiOCH films, and it would show a high WCA of over 160o and a low WCAH of only 2 degrees. Both the hydrocarbon preservation and microstructure were the main factors in improving the surface superhydrophobicity of SiOCH films.MONTPELLIER-BU Sciences (341722106) / SudocSudocFranceF

Surface zwitterionization of PVDF VIPS membranes for oil and water separation

International audienceThis work aims at applying a combined polymerization and membrane surface-modification process, in order to hydrophilize poly(vinylidene fluoride) membranes prepared by vapor-induced phase separation (VIPS), and eventually make them suitable for low transmembrane pressure (Delta P = 0.5 bar) membrane separation of various oil-in-water (O/W) emulsions. Styrene and sulfobetaine monomers were mixed and allowed to react while the PVDF membrane was in contact with the reactive mixture, enabling self-assembling of the random polymer on the membrane as it was formed. Reaction parameters were optimized, and it was found that a solid content of 5 wt%, a styrene/SBMA ratio of 40/60 and a reaction time of 5 h led to very hydrophilic membrane (water contact angle: 12 degrees). The combination of chemical analyses evidenced the successful and controlled surface modification process. Physical analyses showed that deviating from the optimized conditions of styrene/SBMA ratio led to the formation of agglomerates (styrene-rich or SBMA-rich), associated to low porosity, and high coating density. The membranes were used to separate emulsions of toluene/W, hexane/W, hexadecane/W, diesel/W and soybean oil/W, leading to separation efficiency of 99.0%, 99.2%, 99.1%, 99.0% and 99.0%, respectively. This work thus presents a new avenue for surface modification of membrane with extremely efficient copolymers for which there is no common solvent, and brings several evidences of the suitability of VIPS membrane for cost-effective membrane separation of various emulsions

Vacuum-Assisted Interfacial Polymerization Technique for Enhanced Pervaporation Separation Performance of Thin-Film Composite Membranes

In this work, thin-film composite polyamide membranes were fabricated using triethylenetetramine (TETA) and trimesoyl chloride (TMC) following the vacuum-assisted interfacial polymerization (VAIP) method for the pervaporation (PV) dehydration of aqueous isopropanol (IPA) solution. The physical and chemical properties as well as separation performance of the TFCVAIP membranes were compared with the membrane prepared using the traditional interfacial polymerization (TIP) technique (TFCTIP). Characterization results showed that the TFCVAIP membrane had a higher crosslinking degree, higher surface roughness, and denser structure than the TFCTIP membrane. As a result, the TFCVAIP membrane exhibited a higher separation performance in 70 wt.% aqueous IPA solution at 25 °C with permeation flux of 1504 ± 169 g∙m−2∙h−1, water concentration in permeate of 99.26 ± 0.53 wt%, and separation factor of 314 (five times higher than TFCTIP). Moreover, the optimization of IP parameters, such as variation of TETA and TMC concentrations as well as polymerization time for the TFCVAIP membrane, was carried out. The optimum condition in fabricating the TFCVAIP membrane was 0.05 wt.% TETA, 0.1 wt% TMC, and 60 s polymerization time

Evaluation of the Antibacterial Activity of Eco-Friendly Hybrid Composites on the Base of Oyster Shell Powder Modified by Metal Ions and LLDPE

Transforming biological waste into high-value-added materials is currently attracting extensive research interest in the medical and industrial treatment fields. The design and use of new antibacterial systems are urgently needed. In this study, we used discarded oyster shell powder (OSP) to prepare calcium oxide (CaO). CaO was mixed with silver (Ag), zinc (Zn), and copper (Cu) ions as a controlled release and antibacterial system to test the antibacterial activity. The inhibition zones of various modified metals were between 22 and 29 mm for Escherichia coli (E. coli) and between 21 and 24 mm for Staphylococcus aureus (S. aureus). In addition, linear low-density polyethylene (LLDPE) combined with CaO and metal ion forms can be an excellent alternative to a hybrid composite. The strength modulus at 1% LLDPE to LLDPE/CaO Ag increased from 297 to 320 MPa. In addition, the antimicrobial activity of LLDPE/CaO/metal ions against E. coli had an antibacterial effect of about 99.9%. Therefore, this hybrid composite material has good potential as an antibacterial therapy and biomaterial suitable for many applications

AMOC Positron Annihilation Study of Zwitterionic Nanofiltration Membranes: Correlation between Fine Structure and Ultrahigh Permeability

Age–momentum correlation (AMOC) positron annihilation technology was applied for the first time to composite nanofiltration membranes (NFMs) with zwitterionic terpolymers (TPs) to explain their high permeability and high salt selectivity. The NFMs showed an increase in the water flux from 32.6 to 46.3 L m^–2 h^–1 without sacrificing the salt selectivity when the zwitterionic monomer 3-dimethyl­(methacryloyloxyethyl)­ammonium propanesulfonate (DMAPS) content was increased from 0 to 4.35 mol %. The influence of DMAPS content on membrane microstructure, water permeability, and salt selectivity was evaluated by means of AMOC positron annihilation studies. Positron annihilation results showed that the cross-linked TPs selective layer of NFMs was composed of two types of pores: free volume (based on τ₃) with radius of about 3.5–3.1 Å and nanocavity (based on τ₄) with radius of 16.6–46.6 Å. The performance of NFMs depends strongly on the free volume and nanocavity size. The effect of the zwitterionic DMAPS content on the free volume and nanocavity size in NFMs was as follows: the free volume was reduced as the molecular chains were arranged much closer to each other because of the increasing electrostatic interaction, and the nanocavity size was enlarged as the interfacial space was increased as a result of the increased molecular association. NFMs with larger nanocavities and smaller free volume have higher water permeability and higher salt (divalent/monovalent) selectivity

Enhancing Performance of Thin-Film Nanocomposite Membranes by Embedding in Situ Silica Nanoparticles

In this work, silica nanoparticles were produced in situ, to be embedded eventually in the polyamide layer formed during interfacial polymerization for fabricating thin-film nanocomposite membranes with enhanced performance for dehydrating isopropanol solution. The nanoparticles were synthesized through a sol-gel reaction between 3-aminopropyltrimethoxysilane (APTMOS) and 1,3-cyclohexanediamine (CHDA). Two monomers—CHDA (with APTMOS) and trimesoyl chloride—were reacted on a hydrolyzed polyacrylonitrile (hPAN) support. To obtain optimum fabricating conditions, the ratio of APTMOS to CHDA and reaction time were varied. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to illustrate the change in morphology as a result of embedding silica nanoparticles. The optimal conditions for preparing the nanocomposite membrane turned out to be 0.15 (g/g) APTMOS/CHDA and 60 min mixing of APTMOS and CHDA, leading to the following membrane performance: flux = 1071 ± 79 g∙m−2∙h−1, water concentration in permeate = 97.34 ± 0.61%, and separation factor = 85.39. A stable performance was shown by the membrane under different operating conditions, where the water concentration in permeate was more than 90 wt%. Therefore, the embedment of silica nanoparticles generated in situ enhanced the separation efficiency of the membrane