Marek Bryjak

Modification of polysulfone membranes 4. Ammonia plasma treatment

Abstract The effect of NH3 and NH3/Ar plasma on ultrafiltration polysulfone membranes have been studied. Results of contact angle, FTIR–ATR and X-ray photoelectron spectroscopy experiments clearly showed that both plasmas introduced hydrophilic, nitrogen- and oxygen-containing moieties on the polymer surface and that NH3/Ar plasma was more efficient. That plasma was also more aggressive––signs of strong etching could be seen on the SEM pictures. Redeposition of etched material seemed to take place inside the pores. On the contrary, ammonia plasma was soft and caused cleaning the surface and pores enlargement. Performance of ammonia plasma modified membranes was greatly improved and independent on solution pH. The last observation proved amphoteric character of the surface. NH3/Ar plasma treatment gave membranes of acidic surface and filtration indices not so good as for ammonia plasma.

Plasma modified polymers as a support for enzyme immobilization 1. Allyl alcohol plasma

The paper describes deposition of plasma polymerized allyl alcohol on polysulfone film. It is shown that film surface becomes more hydrophilic after plasma treatment independently on presence of argon in a reaction mixture. The chemistry of the new surface layer was established by FTIR-ATR and ESCA spectroscopy. The substrate placed close to the plasma edge was the most hydrophilic but the amount of hydoxyl groups was not the highest there. Presence of argon stabilized the plasma but the deposited layer contained relatively less oxygen-bearing functionalities. The plasma treated polymer was subjected to xylose isomerase immobilization. For this purpose the divinylsulfone method was adapted. The studies revealed no correlation between the surface hydrophilicity and efficiency of immobilization.

Polymeric microspheres with N-methyl-d-glucamine ligands for boron removal from water solution by adsorption-membrane filtration process

Polymeric microspheres with N-methyl-d-glucamine (NMDG) ligands have been tested in the adsorption–membrane filtration process for boron removal from aqueous solutions. The chelating resins were synthesized by reacting NMDG with the vinylbenzyl chloride–styrene–1,4-divinylbenzene (VBC/S/DVB) copolymer at the reflux temperature and in the microwave reactor. VBC/S/DVB spheres with a gel structure that contained 6 wt% DVB were obtained by membrane emulsification followed by suspension polymerization. By selecting the optimal emulsification and polymerization parameters, it was possible to obtain 25-μm-diameter particles with a narrow size distribution. Resins obtained by microwave modification showed the higher boron adsorption capacity.

REMOVAL OF BORON FROM BALÇOVA-IZMIR GEOTHERMAL WATER BY ION EXCHANGE PROCESS: BATCH AND COLUMN STUDIES

In this study, the efficiency of boron removal from Balçova geothermal water provided by the Izmir Geothermal Energy Company, Turkey, has been investigated using boron selective ion exchange resins Diaion CRB 02 and Dowex (XUS 43594.00) by batch and column methods. The results of the column studies have been evaluated in terms of type of resin and feed flow rate, and the effects of particle size and temperature have been investigated using the results obtained from batch kinetic studies. The data from the kinetic studies have been evaluated using pseudo-first-order and pseudo-second-order kinetics models. In addition, the classical diffusion models have been used to evaluate the kinetic data obtained to understand the rate-controlling mechanisms.

Transport of amino acids and their phosphonic acid analogues through supported liquid membranes containing macrocyclic carriers. Experimental parameters

Abstract Amino acid hydrochlorides are well transported through 1-decanol membranes containing Kryptofix 5 or 222 and supported in a porous polyacrylonitrile hollow fiber matrix. Factors which influence the transport of phenylalanine hydrochloride were studied in some detail using this sheet- as well as hollow fibre-supported liquid membranes. These studies show that the choice of the membrane phase, the kind of polymeric support and the mode of membrane preparation are of great importance for the efficiency of the process. The most vital step in the membrane preparation appears to be its activation by soaking in a solution of phenylalanine hydrochloride in a water-ethanol or water-propanol mixture. This probably improves the contact between membrane and the aqueous phase.

Modification of porous polyacrylonitrile membrane

The effects of the modification of polyacrylonitrile ultrafiltration membranes with sodium hydroxide are discussed. The NaOH-induced hydrolysis of nitrile groups on the membrane surface results in membranes with decreasing pore diameter. The average pore diameter changes from 2.6 to 0.6 nm in the progress of hydrolysis. The modified membranes are less prone for protein deposition. Fouling causes a pore diameter reduction of 80% for the untreated and 20% for the modified membranes. Modification results also in the creation of the membranes working in the nanofiltration mode. The unmodified membrane does not reject salt while a membrane immersed in the modification bath is capable of rejecting about 50% of calcium carbonate. Der Einflus einer Modifizierung von Polyacrylnitrilmembranen mit Natriumhydroxid auf die Ultrafiltrationseigenschaften wird diskutiert. Die Hydrolyse der Nitrilgruppen an der Membranoberflache mit NaOH fuhrt zu Membranen mit geringerem Porendurchmesser. Der durchschnittliche Porendurchmesser andert sich im Verlauf der Hydrolyse von 2,6 auf 0,6 nm. Die modifizierten Membranen neigen weniger zur Proteinablagerung. Fouling verursacht bei den unmodifizierten Membranen eine Verringerung des Porendurchmessers um 80% und bei den modifizierten Membranen um 20%. Durch die Modifizierung werden Membranen erhalten, die zur Nanofiltration geeignet sind. Wahrend die unmodifizierten Membranen nicht fahig sind, Salze zuruckzuhalten, konnen die modifizierten Membranen rund 50% Calciumcarbonat separieren.

Effect of Ionic Strength of Solution on Boron Mass Transfer by Ion Exchange Separation

Abstract In the present study, batch kinetic tests have been performed for boron removal from model solutions using boron selective ion exchange resins Diaion CRB 02, Dowex (XUS 43594.00) and Purolite S 108. Several kinetic models have been used to evaluate the sorption kinetics of boron by means of a well mixed stirred system, diffusional models, pseudo‐first‐order, and pseudo‐second‐order kinetic models. The mass transfer model, based on a well stirred system including maximum capacity (Qm, mg/g) and Langmuir constant (b, L/mg) values obtained from Langmuir isotherms, has been used to obtain predictive concentration changes against time. The experimental results have been used to compare with the modelling data for different ionic strength media.

How To Functionalize Ceramics by Perfluoroalkylsilanes for Membrane Separation Process? Properties and Application of Hydrophobized Ceramic Membranes

The combination of microscopic (atomic force microscopy and scanning electron microscopy) and goniometric (static and dynamic measurements) techniques, and surface characterization (surface free energy determination, critical surface tension, liquid entry pressure, hydraulic permeability) was implemented to discuss the influence of perfluoroalkylsilanes structure and grafting time on the physicochemistry of the created hydrophobic surfaces on the titania ceramic membranes of 5 kD and 300 kD. The impact of molecular structure of perfluoroalkylsilanes modifiers (possessing from 6 to 12 carbon atoms in the fluorinated part of the alkyl chain) and the time of the functionalization process in the range of 5 to 35 h was studied. Based on the scanning electron microscopy with energy-dispersive X-ray spectroscopy, it was found that the localization of grafting molecules depends on the membrane pore size (5 kD or 300 kD). In the case of 5 kD titania membranes, modifiers are attached mainly on the surface and only partially inside the membrane pores, whereas, for 300 kD membranes, the perfluoroalkylsilanes molecules are present within the whole porous structure of the membranes. The application of 4 various types of PFAS molecules enabled for interesting observations and remarks. It was explained how to obtain ceramic membrane surfaces with controlled material (contact angle, roughness, contact angle hysteresis) and separation properties. Highly hydrophobic surfaces with low values of contact angle hysteresis and low roughness were obtained. These surfaces possessed also low values of critical surface tension, which means that surfaces are highly resistant to wetting. This finding is crucial in membrane applicability in separation processes. The obtained and characterized hydrophobic membranes were subsequently applied in air-gap membrane distillation processes. All membranes were very efficient in MD processes, showing good transport and selective properties (∼99% of NaCl salt rejection). Depending on the membrane pore size and used modifiers, the permeate flux was in the range of 0.5-4.5 kg·m(-2)·h(-1) and 0.3-4.2 kg·m(-2)·h(-1) for 5 kD and 300 kD membranes, respectively.

Plasma nanostructuring of porous polymer membranes.

Several methods for membrane modification have been presented. Chemical modification of a neat polymer followed by membrane formation and modification of just formed membranes have been compared to plasma action. The following plasma modes are discussed in detail: treatment with non-polymerizable gases, treatment with vapors and plasma initiated grafting. Some examples of modified membrane properties are given. Finally, it was concluded that plasma treatment offers the fastest, environment friendly and versatile method that allows tailoring brand new membranes.

N-butylamine plasma modifying ultrafiltration polysulfone membranes

Abstract Some properties of ultrafiltration polysulfone membranes modified with n-BuNH2 and n-BuNH2/Ar plasmas were studied. Contact angle measurements, XPS and SEM were used to characterize the surface changes. Pore size estimation, water transport and filtration parameters helped to describe changes in filtration performance. Presence of argon in plasma environment stabilized plasma but made it more aggressive; pore size increased and surface etching took place. This plasma grafted a smaller number of nitrogen features — most of them in the form of amine. Excellent filtration performance was observed for BuNH2/Ar plasma-modified membranes in an acidic environment.