Nanoporous β-PVDF membranes with selectively functionalized pores

Cuscito, Olivia; Clochard, Marie-Claude; Esnouf, S.; Betz, N.; Lairez, D.

doi:10.1016/j.nimb.2007.08.089

Cited by 39 publications

(30 citation statements)

References 11 publications

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“…206 There have been three main approaches to construct nanoporous polymer structures (1−100 nm in pore diameter): direct synthesis of nanoporous structures, template-mediated synthesis, and introduction of polymers into mesostructured materials. First, direct synthesis of nanoporous polymer structures can be made by controlled foaming, 207,208 ion track etching, [209][210][211] and phase separation of block copolymers. [212][213][214][215] Krause et al have carried out systematic studies on the physical foaming behavior of polymers using CO 2 as physical blowing gas.…”

Section: Polymer Nanostructuresmentioning

confidence: 99%

Versatile strategies for fabricating polymer nanomaterials with controlled size and morphology

et al. 2008

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The development of reliable synthetic routes to polymer nanomaterials with well-defined size and morphology is a critical research topic in contemporary materials science. The ability to generate nanometer-sized polymer materials can offer unprecedented, interesting insights into the physical and chemical properties of the corresponding materials. In addition, control over shape and geometry of polymer nanoparticles affords versatile polymer nanostructures, encompassing nanospheres, core-shell nanoparticles, hollow nanoparticles, nanorods/ fibers, nanotubes, and nanoporous materials. This review summarizes a diverse range of synthetic methods (broadly, hard template synthesis, soft template synthesis, and template-free synthesis) for fabricating polymer nanomaterials. The basic concepts and significant issues with respect to the synthetic strategies and tools are briefly introduced, and the examples of some of the outstanding research are highlighted. Our aim is to present a comprehensive review of research activities that concentrate on fabrication of various kinds of polymer nanoparticles.

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Section: Polymer Nanostructuresmentioning

confidence: 99%

Versatile strategies for fabricating polymer nanomaterials with controlled size and morphology

et al. 2008

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“…The synthesis of functionalized radio grafted -PVDF membranes was developed at the Laboratoire des Solides Irradies. 24,[27][28][29][30][31][32] -PVDF polymer films are first bombarded by swift heavy ions, figure 2a, and the tracks formed along the ion passage are revealed under alkaline chemical treatment, figure 2b. The obtained nanoporous polymer membranes do not need to undergo subsequent e-beam irradiation to increase radicals in the polymer bulk for submicron pore diameters.…”

Section: Resultsmentioning

confidence: 99%

Functionalized nanoporous track-etched β-PVDF membrane electrodes for lead(ii) determination by square wave anodic stripping voltammetry

et al. 2011

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Track-etched functionalized nanoporous -PVDF membrane electrodes, or functionalized membrane electrodes (FME), are thin-layer cells made from track-etched, poly(acrylic acid) (PAA) functionalized nanoporous -poly(vinylidene fluoride) (-PVDF) membranes with thin Au films sputtered on each side as electrodes. The Au film is thin enough that the pores of the membranes are not completely covered. The PAA functionalization is specifically localised in the walls of the nanoporous -PVDF membrane by radio grafting. The PAA is a cation exchange polymer that adsorbes metal ions, such as Pb 2+ , from aqueous solutions thus concentrating the ions into the membrane. After a calibrated time the FME is transferred to an electrochemical cell for analysis. A negative potential is applied to the Au film of the FME for a set time to reduce the adsorbed ions onto the Au film working electrode. The other metalized side of the FME functions as a counter electrode. Finally, square-wave anodic stripping voltammetry (SW-ASV) is performed on the FME to determine the metal ion concentrations in the original solution based on calibration. The calibration curve of charge versus log concentration has a Temkin isotherm form. The FME membranes are 9 m thick and have 40 nm diameter pores with a density of 10 10 pores/cm 2. This high pore density provides a large capacity for ion adsorption. Au ingress in the pores during sputtering forms a random array of nanoelectrodes. Like surface modified electrodes for adsorptive stripping voltammetry, the pre-concentration step for the FME is performed at open circuit. The zero current intercept of the calibration for Pb 2+ is 0.13 ppb (g/L) and a detection limit of 0.050 ppb based on 3S/N from blank measurements. Voltammetry (CV) and chronoapmerometry (CA) were used to characterize the system. The apparent diffusion coefficient (D) for Pb 2+ in the PAA functionalized pores was determined to be 2.44 x 10-7 cm 2 /s and the partition coefficient (pK M) was determined to be 3.08. The maximum allowable levels for toxic metals in water are now set at low ppb (g/L) levels. The maximum levels of Pb 2+ in potable water established the European Environmental Agency (EEA) the United States Environmental Protection Agency (EPA) and recommendations from the World health Organisation (WHO) are 7.2, 15.0, and 10.0 ppb respectively and the goal of the United States EPA is zero. 1-3 Reliable quantification of these low concentrations is difficult time consuming and expensive. Also, the analysis equipment is not portable so the samples have to be sent a centralised lab which typically involves a 24 hour turn around time, which means that pollution events can be missed, or detected too late. Electrochemical analysis techniques, such as anodic stripping voltammetry (ASV), are generally inexpensive, rapid and portable. The electrode of choice for measuring trace levels of toxic metal ions by ASV has been the dropping mercury electrodes (DME). 4 DMEs and mercury film electrodes are very sensitive, due to their high capa...

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“…radical fraction present on the pore walls after etching depends on the track diameter as their density decreases as 1/R 2 (R the etched track radius) from the initial track core (Barsbay et al, 2013). As previously described (Cuscito et al, 2007;Barsbay et al, 2013), the diameter is proportional to the etching time. However the linear relationship also depends on the fluence.…”

Section: Etched Ion Track Graftingmentioning

confidence: 86%

“…A strong alkaline solution (KOH 10 N) in synergy with an oxidant such as KMnO 4 is needed to reveal the tracks into cylindrical nanopores under our experimental conditions. In PVDF, the residual radicals formed during irradiation all along the tracks are still present in the pore walls after etching when the diameters are less than a few hundred nm (Cuscito et al, 2007). These radicals trapped in the crystallites of PVDF are able to initiate a polymerization in the presence of a vinyl monomer such as acrylic acid with a maximum efficiency and reproducibility at a diameter of 50 nm (Barsbay et al, 2013).…”

Section: Synthesis Of Nanoporous Mercury-sensitive Membranesmentioning

confidence: 99%

Poly(4-vinyl pyridine) radiografted PVDF track etched membranes as sensors for monitoring trace mercury in water

Bessbousse

Zran

Fauléau

et al. 2016

Radiation Physics and Chemistry

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International audiencePoly-4-vinyl pyridine chains were radiografted inside the etched-tracks of PVDF nanoporous membrane. P4VP grafting was found to be localized on the solid PVDF surface. Coating of these PVDF-g-P4VP membranes with a very thin layer of gold results in an ASV electrochemical sensor. Functionalized ion track-etched PVDF-g-P4VP sensors were found very selective and highly sensitive for mercury LOD 5 ng/L. a b s t r a c t By a radiation-induced grafting technique, we have functionalized track-etched nanoporous polymer membranes with mercury sensitive poly-4-vinyl pyridine (P4VP). Coating of these membranes with a very thin layer of gold results in an electrochemical sensor that is very selective and highly sensitive for mercury LOD 5 ng/L – well below the norms for water (0.015 mg/L potable water and 0.5 mg/L residual waters-French water norms of 27 October 2011). E-beam irradiation permitted optimization of the radiografting synthesis on PVDF thin films prior to ion-track grafting. Synthesis and characterization by EPR, FESEM and FTIR are described in detail. A comparison between FTIR in ATR and transmission modes enabled us to localize the grafting on the surface of the e-beam irradiated PVDF films allowing us to extrapolate what happens on the etched tracks. Using Square Wave Anodic Stripping Voltammetry (SW-ASV), mercury concentrations of 1 mg/L are detected in 2 h and low ng/L concentrations are detected after 24 h of adsorption. The adsorption is passive so sensors do not require instrumentation and the analysis takes only 3–4 min. Also, the P4VP functionalized sensor appears insensitive to pH variations (pHs 3–9), high salt concentrations (up to 1 g/ L) and the presence of other heavy metals in the same solution.

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Nanoporous β-PVDF membranes with selectively functionalized pores

Cited by 39 publications

References 11 publications

Versatile strategies for fabricating polymer nanomaterials with controlled size and morphology

Versatile strategies for fabricating polymer nanomaterials with controlled size and morphology

Functionalized nanoporous track-etched β-PVDF membrane electrodes for lead(ii) determination by square wave anodic stripping voltammetry

Poly(4-vinyl pyridine) radiografted PVDF track etched membranes as sensors for monitoring trace mercury in water

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