Permeability and chemical analysis of aromatic polyamide based membranes exposed to sodium hypochlorite

In this study, a cross-linked aromatic polyamide based reverse osmosis membrane was exposed to variable sodium hypochlorite ageing conditions (free chlorine concentration, solution pH) and the resulting evolutions of membrane surface chemical and structural properties were monitored. Elemental and surface chemical analysis performed using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR), showed that chlorine is essentially incorporated on the polyamide layer of a commercially available composite RO membrane, when soaked in chlorine baths, presumably through a two step electrophilic substitution reaction governed by the concentration of hypochlorous acid (HOCl), at pH values above 5. Deconvolution of the FTIR vibrational amide I band experimentally confirmed previous assumptions stated in the literature regarding the weakening of polyamide intermolecular hydrogen bond interactions with the incorporation of chlorine. An increase in the fraction of non associated Cdouble bond; length as m-dashO groups (1680 cm−1) and a decrease of hydrogen bonded Cdouble bond; length as m-dashO groups (1660 cm−1) were observed with an increase in the concentration of the free chlorine active specie. The relative evolution of pure water permeability was assessed during lab-scale filtration of MilliQ water of a membrane before and after exposure to chlorine. Filtration results indicate polyamide conformational order changes, associated with the weakening of polyamide intermolecular H bonds, as observed with the increase in the packing propensity of the membrane, dominant for HOCl doses above 400 ppm h. In addition, water–sodium chloride selectivity capabilities permanently decreased above this HOCl concentration threshold, further suggesting polyamide chain mobility. However, under controlled exposure conditions, i.e., HOCl concentration, operating conditions (applied pressure or permeation flux) can be improved while maintaining similar RO membrane separation performance

Mass transfer properties of chlorinated aromatic polyamide reverse osmosis membranes

Water (A) and solute (B) permeability of aromatic polyamide (PA) reverse osmosis membranes (RO) were monitored under varying applied pressure, solute nature and concentration to assess their evolution after exposure of the membrane to free chlorine. Above a threshold value of 400 ppm h HOCl water permeability was influenced by permeation conditions during both filtration of ultrapure water (UP water) and reverse osmosis of salts performed sequentially. Water permeability decreased during the filtration of UP water performed at a constant applied pressure of 60 bar. During the reverse osmosis of an electrolyte solution, performed at a constant permeation flux of 31 L h¯¹ m¯², A was observed to increase continuously with time, e.g. up to a factor of 3 after exposure to 3120 ppm h HOCl, most severe dose used. Differences in the charge density of mono- and divalent cations did not influence the rate of increase of A with time, which was however shown to depend on salt flux and ascribed to a diffusion limited relaxation process presumed to occur within the dense hydrated PA network. The relative and opposite impact of applied pressure and of salt permeation highlighted the importance in distinguishing conditions under which the water permeability (A) of a chlorinated membrane is measured, whether during the filtration of UP water or of a salt

Characterisation of aged HDPE pipes from drinking water distribution : investigation of crack depth by Nol ring tests under creep loading

International audienceHDPE pipes are used for the transport of drinking water. However, disinfectants in waterseem to have a strong impact on their mechanical behaviour, limiting their lifetime inoperation. Indeed, oxidation occurs when they are in contact with disinfectants leading to theformation of a thin oxidised layer coupled to the cracks initiation of cracks of different lengthsfrom the inner wall surface. An original method is proposed here to characterise the ageingeffect of the pipe mechanical behaviour. Inspired from the ASTM D 2290-04 standard, NolRing tests have been performed under tensile and creep loadings on smooth rings. Aconstitutive equation has been determined from these tests using a finite element (FE)modelling. FE simulations have been performed to study the influence of the thin oxidised PElayer. Precracked specimens with different crack depth ratio have also been modelled. Thecrack depth ratio is an important parameter to quantify pipe ageing

Mechano-chemical ageing of PES/PVP ultrafiltration membranes used in drinking water production

In water treatment by microfiltration and ultrafiltration, a major concern is the integrity loss or failure of membrane induced by onsite operations, potentially leading to permeate water contamination. This study aims to provide a better understanding of the phenomena responsible for membrane damage by analyzing its causes and effects. The role of sodium hypochlorite exposure conditions and the impact of mechanical stress on membrane characteristics were investigated. Monitoring of hydraulic response, mechanical properties and the evolution of the chemical structure showed, on multiple scales, strong indications of membrane chemical degradation, involving radical mechanisms, accelerated by tensile stress application

Fracture mechanics of creeping solids applied to pre-cracked NOL ring specimens to predict residual lifetime of high density polyethylene pipes

International audienceHigh Density Polyethylene (HDPE) is widely used for the distribution of drinking water and are exposed to an internal pressure due to water flow. Furthermore, when they are in contact with disinfectants, oxidation of HDPE occurs at the immediate surface of the inner wall. This leads to a decrease in the HDPE molar mass and consequently, to a hardening as well as an embrittlement of the material. The oxidised layer thickness seems to stabilize at 200 μm whatever the initial pipe thickness due to the diffusion of reactive species in the inner wall. Inspections with a scanning electron microscope (SEM) of the inner wall of pipes collected on site, after several years of service, showed a network of cracks. The most noxious (deepest) longitudinal crack propagates under the steady internal pressure until the complete failure of the pipe. The experimental investigations consisted of creep crack growth tests, carried out on an original geometry for this type of test using NOL ring. These specimens were cut from the pipes and an internal longitudinal crack implanted. Creep crack growth tests were performed at various net stresses and at various crack depth ratios. At the end of each test, the time to failure was recorded. Before applying the theory of fracture mechanics of creeping solids, 3D finite element simulations were carried out to assess the suitability of assuming plane strain conditions. To this end, a porous viscoplastic model was implemented into an in-house finite element code. A fracture criterion based on critical porosity allowed for the simulation of creep crack growth. The localization of the maximum damage at mid-thickness and the thickness reduction were well captured. In these conditions, the crack front curvature is located near the surface so that a 2D calculation with plane strain conditions can then be justified to determine the C* load parameter. The residual lifetime of a real pipe containing a longitudinal defect, under in-service loading was estimated by using the correlation between the time to failure and the C*-integral

Multi-scale analysis of hypochlorite induced PES/PVP ultrafiltration membranes degradation

In drinking water production plants, the use of oxidants such as sodium hypochlorite during in-place cleanings may impair the membrane integrity and radically impact the ultrafiltration process efficiency, leading to potential contamination of the permeate water with pathogens. This study investigates the effects of hypochlorite exposure on the properties of a commercially available UF hollow fiber. Mechanical performances and water permeability appeared to be greatly affected by the contact with hypochlorite. Monitoring them olecular changes by X-rayphoto electron spectroscopy (XPS), attenuated total reflectance infraredspectroscopy (ATR-IR), size exclusion chromatography (SEC) and VITA-mode atomic forcemicroscopy (VITA-AFM) revealed high stability of the main polymer constituting the membrane (i.e. polyethersulfone (PES)) and very high reactivity of the additive (i.e. poly (N-vinyl pyrrolidone (PVP)) towards immersion in aqueous sodium hypochlorite solution with maximal reaction rate for neutral to slightly basic pH. Correlation of those results unexpectedly leads to the conclusion that the over all membrane properties changes are governed by the additive fate

Kinetics of chlorine-induced polyethylene degradation in water pipes

The presence of chlorine in drinking water supplies in many countries creates the undesirable side effect of causing a relatively under investigated degree of polymer degradation in the polyethylene pipes used for transport. In order to predict pipe lifetimes and ensure safe water supplies, a kinetic model using data for the degradation rates of polyethylenes immersed in chlorine solutions, was developed. In order to replicate phenomena that normally occur very slowly at low concentrations of chlorine, accelerated ageing studies were necessary. These were carried out at high chlorine concentrations under well-defined experimental conditions (70, 400 and 4000 ppm). Results showed that, for the chlorine concentrations studied, a chain scission process associated with carbonyl formation is occurring. It was also shown that the rate of this degradation does not depend on the presence of stabilizer. A kinetic model, taking into account the chlorine concentration, is proposed in order to simulate the molar mass changes occurring. This will facilitate the prediction of the degree of polyethylene embrittlement and ultimately the lifetime

Pilot scale study of chlorination-induced transport property changes of a seawater reverse osmosis membrane

A pilot-scale study was performed to assess variations of reverse osmosis (RO) membrane water permeance (A) and salt retention (Robs) induced by chlorination and to compare them with those observed at the lab-scale. A chlorination protocol was adapted to expose only the surface active layer (an aromatic polyamide)of a composite RO membrane to consecutive free chlorine doses ranging from 40 to 4000 ppm h, at pH 6.9. Along the long-term filtration of seawater, performed with a 4" spiral wound RO module, we monitored the variations of A, the decrease of Robs and the rate of increase of A with time, and found themquantitatively similar to those reported in previous studies performed at the lab-scale under accelerated exposure conditions. The elemental analysis of the feed and permeate streams revealed that the rejection of divalent ions remained constant (ca. 100%), irrespective of the free chlorine dose reached, whereas the rejection of monovalent ions of the seawater (mainly sodium, chloride and bromide ions) decreased as the exposure dose increased. Overall, transposing the characterization procedure to the pilot-scale further supports that chlorination of PA, under pH conditions usually found in desalination plants (6.9 to 8.0), is controlled by the concentration of HOCl, as observed from elemental analysis of the surface by XPS

Caractérisation et vieillissement d'une membrane d'ultrafiltration d'eau

During disinfections, water ultrafiltration membranes are mechanically and chemically stressed. These stresses lead to an early membrane ageing implying a drop of the quality of ultrafiltrated water. The aim of this study is to examine the long term behaviour of an ultrafiltration polysulfone hollow fibre in contact with bleach. After the initial characterisation of the fibre and its main component (polysulfone), we broached watermembrane physical interaction. The sorption behaviour of this asymmetric membrane could be interpreted within a dual mechanism constituted of two simultaneous phenomena: pore filling and water absorptiondiffusion in the pore walls. As chemical ageing could induce large modifications on membranes interaction and transport properties, we studied these phenomena via structure-properties relationships. The bleach-membrane chemical interaction shows a degradation of the polysulfone, in spite its well-known chemical stability. The degradation, which generates an embrittlement of the fibre, occurs by chains scission (determined by Size Exclusion Chromatography) with the hydroxyl radical - OH formed in the bleach solution. These chain scissions take place on the isopropylidene and sulfone groups to form final vinylidene and sulfonate groups respectively. Analytic investigations (IR and proton NMR) show that the degradation of additives happens separately without interfering on the ageing of the PSU but alters the behaviour of the fibre. The lifetime of the fibre depends on the total chlorine concentration of the ageing solution but also on its pH which drives the formation of hypochlorous acid and hypochlorite ion in great proportion, essential condition for the formation of hydroxyl radicals.Sur site, les membranes d'ultrafiltration d'eau sont soumises à des sollicitations mécaniques et chimiques lors de leur désinfection. Ces sollicitations conduisent à un vieillissement précoce de la membrane pouvant aller jusqu'à la rupture mécanique et générer une baisse de la qualité de l'eau ultrafiltrée. Le but de cette étude est d'examiner le comportement à long terme d'une fibre creuse d'ultrafiltration au contact d'une solution d'eau de Javel. Après une caractérisation initiale de la fibre et de son constituant majoritaire, le polysulfone, nous avons étudié les interactions physiques de cette membrane avec l'eau. Le comportement en sorption de cette fibre asymétrique doit être considéré comme un mécanisme dual constitué de deux phénomènes simultanés : remplissage des pores et absorption-diffusion de l'eau dans les parois des pores. Le vieillissement chimique, engendré par la désinfection des fibres, est susceptible de modifier les propriétés d'interaction et de transport de l'eau dans les parois et ainsi affecter les propriétés d'utilisation des membranes. Il nous a donc paru nécessaire de bien comprendre ces phénomènes, et ce par le biais des relations structure-propriétés. L'étude de l'interaction chimique membrane-eau de Javel, a permis, quant à elle, de mettre en évidence une dégradation du PSU en immersion, réfutant sa stabilité chimique reconnue. Cette dégradation, à l'origine de la fragilisation de la membrane, se produit par coupure de la chaîne principale du PSU (mise en évidence par chromatographie d'exclusion stérique) sous l'action du radical - OH formé au sein de la solution de Javel. Ces ruptures se produisent au niveau des groupements isopropylidènes et sulfones et forment respectivement des groupements vinylidènes et sulfonates terminaux. Les investigations analytiques (IR et RMN 1H) montrent que la dégradation des additifs contenus dans la fibre (agents hydrophile et porogène) se produit indépendamment sans interférer avec le vieillissement du PSU, mais altère néanmoins le comportement de la fibre. La durée de vie de la fibre dépend non seulement de la concentration en chlore total de la solution de lavage mais également de son pH qui conditionne la formation en proportion significative des espèces HClO (acide hypochloreux) et ClO- (ion hypochlorite), indispensables pour la formation des radicaux hydroxyles