Recent trends in extraction and transport of metal ions using polymer inclusion membranes (PIMs)

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Abstract

The interest around polymer inclusion membranes (PIMs) has grown considerably in the past 6 years and, as a result, the number of research papers has risen exponentially. PIMs have been demonstrated to be useful for the selective extraction and recovery of numerous cations and anions and mimic the extraction properties of traditional solvent extraction and ion-exchange processes but have the advantage that extraction and back-extraction can be achieved in a single step. This review provides an overview of PIMs studies reported since 2005 and discusses extraction and transport studies according to the various base polymers, carriers, plasticizers and modifiers that have been used. Also discussed are the investigations of the PIM structure and stability in relation to other liquid membranes and the extension of the application of PIMs to separation problems involving analytical chemistry techniques such as flow analysis and analyte preconcentration.

Highlights

▸ Research on polymer inclusion membranes (PIMs) since 2005 has been reviewed. ▸ A typical PIM consists of a base polymer and a carrier (extractant). ▸ In some cases a plasticizer or modifier may be added to the PIM composition. ▸ The effect of the composition of PIMs on their separation properties is discussed. ▸ An overview of PIM structural studies and analytical applications is presented.

Introduction

Previously, in our review published in 2006 we described the various types of membranes that can be used in membrane-based processes and we made polymer inclusion membranes (PIMs) the focus of that review [1]. Since then there has been an escalation of the number of research papers published on PIMs as indicated in Fig. 1, which shows the number of papers published per year since 1967. Thus, we felt it timely to update our previous review by describing the papers on PIMs published over the past six years (until March 2012). The influence of PIMs composition on their physical and chemical characteristics, membrane selectivity and transport efficiency are important issues discussed in the current review.

The polymer-based liquid membrane concept has been known for over 40 years and has been proposed as a possible alternative to conventional solvent extraction. It has also been used in preparing the sensing membranes in ion-selective electrodes. However, more recently, such membranes have been termed polymer inclusion membranes (PIMs) and have been shown to exhibit excellent stability and versatility, particularly when compared to other liquid membrane types (e.g., supported liquid membranes (SLMs)).

PIMs are usually composed of an extractant (carrier), a base polymer (commonly poly(vinyl chloride) (PVC) or cellulose triacetate (CTA)) and a plasticizer or modifier. The carrier is essentially a complexing agent or an ion-exchanger, responsible for binding with the species of interest and transporting it across the PIM. This process relies on the concentration gradient of the species/carrier complex or ion-pair formed within the membrane, which acts as the driving force enabling transport across the membrane. The base polymer provides the membrane with mechanical strength and the plasticizer provides elasticity and flexibility. The plasticizer decreases the glass transition temperature of the membrane and improves the compatibility of the membrane components. In some cases, the carrier also acts as a plasticizer and so an additional plasticizer is not necessary. A modifier is occasionally added to the membrane composition to improve the solubility of the extracted species in the membrane liquid phase. Recently, Pereira et al. [2] described several compatible combinations of frequently used base polymers and extractants and discussed the factors influencing the homogeneity, flexibility and mechanical strength of PIMs.

Section snippets

Basic carriers

Basic carriers in PIMs consist mainly of amine-based compounds such as quaternary ammonium salts and tertiary amines. Table 1 lists a number of these carriers that have been studied recently along with the base polymer and plasticizer/modifier used in the PIM composition and the target species. This section includes a description of these studies. It should be noted that the membrane compositions quoted throughout this review are in mass percentages.

Aliquat 336 is a commercial solvent

Base polymers

PVC and CTA are still the most widely used base polymers in PIMs since they provide a high mechanical strength to the membranes and are compatible with most carriers. Nevertheless, only a few studies have recently been focused on the effect of their properties on the performance of PIMs.

Fontàs et al. [12] studied PVC and CTA as base polymers in PIMs containing Aliquat 336 as the carrier and NPOE as the plasticizer for the preconcentration of Cr(VI). Results revealed that the polymer matrix did

Plasticizers

It should be noted that Aliquat 336 is a good plasticizer for PVC as are some other frequently used carriers such as D2EHPA and TBP. However, in many cases a plasticizer or modifier is additionally incorporated in the membrane preparation in order to improve the PIM flexibility and the compatibility between the membrane components (i.e., base polymer, carrier and carrier/extracted species complex or ion-pair). NPOE and NPPE are among the most commonly used plasticizers and several recent PIM

Morphology and structure

Several advanced and sophisticated techniques have been employed in the study of the morphology and structure of PIMs with the aim of establishing whether the membranes are truly homogeneous or have a micro-porous structure where the pores are simply filled with the membrane liquid phase in a similar way to SLMs. Most studies involving PIMs report that the membranes are homogeneous, however, this is mainly based on the rather subjective observation that the membranes look transparent and

Conclusions and future trends

Recent research on PIMs, as discussed in this review, demonstrates a steady increase in the interest in these membranes as evidenced by the rising number of research articles being published each year. Many of the well known commercial SX reagents used in large scale separation systems remain of great interest which is no doubt due to the fact that the SX systems require a large inventory of highly flammable diluents as well as extractants whereas membranes do not. Also, the losses to the

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