Recent Advance of Inorganic Fillers in Mixed Matrix Membrane For Gas Separation

Separation and Purication Technology 81 (2011) 243264
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Separation and Purication Technology

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Review
Recent advances of inorganic llers in mixed matrix membrane for gas separation
P.S. Goh a, A.F. Ismail a,b,, S.M. Sanip a,b, B.C. Ng a, M. Aziz a,c
a
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia Faculty of Petroleum and Renewable Energy Engineering, Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia c Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia
b
a r t i c l e
i n f o
a b s t r a c t
Mixed matrix membrane (MMM) is a new class of membrane materials that offers the signicant potential in advancing the current membrane-based separation technology. As an attractive material that demonstrates outstanding separation properties, MMM has been the subject of worldwide academic studies conducted by many researchers especially those related to membrane technology. The past decades have witnessed substantial progress and exciting breakthroughs in both the fundamental and application aspect of MMM in various forms of separation, particularly in gas separation. These emerging materials for separation have been traditionally accomplished by incorporating conventional inorganic llers such as zeolite, carbon molecular sieve and silica nanoparticles in a polymer matrix. The recent advances have shifted towards the introduction of new and novel materials namely carbon nanotubes, metal organic framework and clay layered silicate as potential llers in the polymer matrix. The successful implementation of MMM depends greatly on the polymer matrix selection, the inorganic ller as well as the interaction between the two phases. The selection of suitable types of inorganic ller, the surface modication, and the performance of the resulted MMM membranes were discussed and represented the major contribution in this review. The recent efforts to tackle the underlying problems and the effects of various kinds of modication that would eventually heighten the performance of membrane applications in gas separations were discussed. Better understanding on the improvement and optimization of MMM process was provided by considering the possible solutions to overcome the problems encountered during MMM preparation. This hybrid system holds signicant potential and great promise for further investigations, development and applications. The future direction and perspective in MMM research for gas separation was also briey outlined to further advance the materials for MMM in gas separation. 2011 Elsevier B.V. All rights reserved.
Article history: Received 8 June 2011 Received in revised form 26 July 2011 Accepted 31 July 2011 Available online 6 August 2011 Keywords: Mixed matrix membranes Gas separation Inorganic llers
Contents 1. 2. 3. 4. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mixed matrix membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Inorganic fillers as dispersed phase in MMMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conventional fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Carbon molecular sieve. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Silica. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4. Metal oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Alternative fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2. Layered silicate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3. Metal organic framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . New and emerging material for MMM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion and future direction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244 245 246 247 247 249 250 252 253 253 256 258 260 260 261
5.
6. 7.
Corresponding author at: Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia. Tel.: +60 7 5535592; fax: +60 7 5581463. E-mail address: afauzi@utm.my (A.F. Ismail).
1383-5866/$ - see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2011.07.042
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P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
1. Introduction Membrane technology is an attractive separation approach that has been studied extensively as a result of the fast and energy efcient process without any phase changes [13]. Membrane-based separation involves the use of membrane as a thin barrier between miscible uids to separate a mixture. This interface may be molecularly homogeneous in which it is completely uniform in composition and structure, or it may be chemically or physically heterogeneous in which pores or layered structures are formed. During the separation processes, a suitable force such as concentration or pressure differential is applied to allow preferential transport of one or more feed component across the membrane. Generally, the permeation and selectivity are the two common basic performance characteristics of a membrane. In a broader context of denition, the permeability is the ability of the permeates to pass through a membrane meanwhile the ratio of permeability of the more permeable component to that of the less permeable is known as selectivity of the membrane. Higher permeability decreases the amount of membrane area required to treat a given amount of gas, thereby decreasing the capital cost of membrane units meanwhile higher selectivity will result in a higher purity gas product. Membrane is a promising candidate for separation due to the advantages offered by the process which include high stability and efciency, low operating cost and capital, low energy requirement and also ease of operation [47]. Furthermore, it is also known for its reliability to be used in remote locations as membrane has no moving parts and thus making it mechanically robust. Since the last few decades, membrane-based separation has emerged as a promising process for various industrial applications, particularly in gas separation industries for air separation, hydrogen recovery and CO2 removal [8]. Other well established membrane processes in chemical and petrochemical industries are listed in Table 1. One of the most important characteristics of membranes is the ability to control the rate of permeation of different species. The mechanism of permeation can be described using two models, i.e. solution-diffusion model and pore-ow model [9]. Diffusion is the basis of the solution-diffusion model in which the permeable components dissolve in the membrane materials and then transport across by a concentration gradient. On the other hand, the pore-ow model describes the transportation of permeable components by pressure-driven convection ow through tiny pores in the membrane materials. In general, two types of gas separation processes have been encountered, i.e. gas permeation and
Table 1 Various applications of membrane-based gas separation in industries. Gas separation O2/N2 H2/hydrocarbon H2/N2 H2/CO CO2/hydrocarbon H2O/hydrocarbon H2S/hydrocarbon He/hydrocarbon He/N2 Hydrocarbon/air H2O/air Applications Oxygen enrichment, inert gas generation Renery hydrogen recovery Ammonia purge gas Syngas ratio adjustment Acid gas treatment, greenhouse gas capture Natural gas dehydration Sour gas treating Helium separation Helium recovery Hydrocarbon recovery Air dehumidication
gas diffusion. The former process is of great industrial interest where it is a pressure driven process in which the vapor components pass through a non-porous membrane by a solution-diffusion mechanism. Meanwhile, gas diffusion process can be done for the microporous membranes that operate under a concentration or partial pressure gradient. The successful application of membranes in an identied gas separation process, in both lab and industrial scale, greatly depends upon the selection of membrane materials with the appropriate chemical, mechanical and permeation properties. The major issue of current membrane manufacturing to researchers is to develop highly selective and permeable membrane materials which also show sufcient resistance towards the feed components as well as towards the operation condition [10]. Gas separation using polymeric membrane has achieved important success as high separation performance membrane since the rst commercial-scale membrane gas separation system which was produced in the late 1970s [11]. Polymeric membranes, particularly those prepared from glassy polymers, have received considerable attention because they possess advantages of mechanical properties, reproducibility and relative economical processing capability [12]. Polymeric membranes can be classied as: porous and nonporous membranes. A porous membrane has rigid, highly voided structure with randomly distributed, interconnected pores. Separation in these kinds of membranes is dependent on both the molecular size and pore size distribution. Non-porous membranes or dense membranes consist of a dense lm in which the permeate molecules are absorbed and followed by diffusion through the membrane matrix under the driving force of a pressure, concentration, or electrical potential gradient. The diffusivity and solubility of the permeant molecules in the membrane material play a significant role to determine the mechanism of the gas transport. Among the many types of polymers that exhibit gas separation properties for gas mixtures, a few glassy polymers such as polysulfone (PSf), polyethersulfone (PESf), polyetherimide (PEI) and polyimide (PI) have been recognized as promising polymers with respect to their permeability and selectivity. Despite their suitability for various applications in research and commercialization, polymeric membranes are still ineffective in meeting the requirement for the current advanced membrane technology as these materials have demonstrated a trade-off between the permeability and selectivity, with an upper-bound evident as proposed by Robeson. A correlation of membrane separation data offering an analysis of the limits of polymer permeability and selectivity is often referred to as the upper boundary in which the gas separation properties of the polymeric membranes follow distinct trade-off relations where more permeable polymers are generally less selective and vice versa [13,14]. The revisited upper bound relationship by Robeson for O2/N2 membrane separation for polymeric membranes is illustrated in Fig. 1 [15]. Apart from that, polymeric membranes are also suffering in their limited solvent and poor chemical and thermal resistance, as well as the occurrence of swelling phenomenon that subsequently alter the membrane separation properties [16]. Due to the susceptibility of polymeric membranes to chemical degradation and thermal instability, their applications have been limited to separation processes where hot reactive gases are not encountered. In order to combat the inherent limitations of polymeric membrane, research is underway for alternative membrane materials. In this context, inorganic membranes that are formed from metals, ceramic or pyrolyzed carbon has attracted global
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(a)
Dense structure Inorganic fillers
(b)
Support layer
Dense skin
Fig. 2. Mixed matrix membranes in conguration: (a) symmetric at dense mixed matrix membrane. (b) Asymmetric hollow ber.
Fig. 1. Revisited upper bound data for O2/N2 membrane separation [15].
interest as they offer several advantages over the polymeric membranes for many gas separation processes. Inorganic membranes are increasingly being explored due to their attractive characteristics and advantages over the polymeric membranes [1720]. In general, inorganic membranes can be categorized as dense and porous. Porous inorganic membranes such as zeolite and carbon molecular sieve (CMS) are favourable, rendered by their excellent selectivity which is signicantly higher compared to that of polymeric membranes. Dense inorganic membranes possess very specic separation behaviours, for example metallic membranes that are hydrogen or oxygen specic [21]. The ability to withstand high temperature for long time and the resistance to harsh operation environment have shown promise for application in membrane reactors for many industrial processes. Besides having these robust characteristics, inorganic membranes also have much higher throughput and longer life span compared to polymeric membranes. While attracting considerable attention in many industrial processes, some disadvantages exhibited by inorganic membranes are very critical and serious to be addressed. Although some inorganic materials display properties well above the trade-off curve for polymers, such properties are challenging to duplicate in large-scale modules containing thousands of square meters of membrane areas as it involves expensive capital and repairing cost. Furthermore, the nature of inorganic membrane that is brittle and normally with low surface-to-volume ratio has also hampered the full optimisation of this material for industrial applications [17]. Many new attempts have been made to overcome the limitation of polymeric and inorganic membranes. Introduction of new membrane materials is still a big challenge to be researched in this frontier technology, with most researchers looking at techniques to enhance the separation processes. So called mixed matrix membrane (MMM), where inorganic llers are dispersed at a nanometer level in a polymer matrix have been identied to potentially provide a solution to the trade-off issues of the polymeric membrane, as well as solving the inherent brittleness problems found in inorganic membranes, is illustrated in Fig. 2. The choice of the polymer, inorganic phase and ller particle loading are some of the important parameters affecting the morphology and performance of the MMM. The successful implementation of the further development of MMM greatly lies on these parameters. In order to choose the appropriate continuous polymer phase and dispersed inorganic
phase, the transport mechanisms and the gas component preferentially transporting through the membranes should be rst taken into consideration [22]. To obtain remarkably well performing MMM that surpass the intrinsic properties of the polymer matrix, the role of inorganic ller as the molecular sieve that favors one component while hindering other components to pass through it is of importance. Molecular sieves such as zeolite and CMS have been conventionally packed in the polymer phase to form a dense region of mixed matrix layer. These nanoporous materials possess the shape and size selective nature and hence allow molecular sieving discrimination by permitting smaller sized penetrates to diffuse at higher rate than that of larger sized. Recently, alternative nano-structured materials such as carbon nanotubes (CNTs), clay and metal organic framework (MOF) have also found their excellent sieving characteristic in the fabrication of MMM. However, despite the promising application of these materials as inorganic ller, the existence of adequate contact between the polymer phase and dispersed ller to eliminate the interfacial defects is always a major issue to be addressed in order to achieve the desired as well as improved performance of the resulting MMM. The current contribution reviews recent scientic and technologically advances in the application of different types of inorganic ller materials in the fabrication of MMM. As a review of the stateof-the-art in MMM using various kinds of llers, the progress that has already been made so far will be explored. The membrane properties, particularly gas separation performance of the MMM using both conventional and alternative materials as the inorganic phase are highlighted and discussed. This review article is meant to stimulate the interest and enthusiasm towards the currently wellidentied as well as the under exploration research on MMM among the membrane research community. Aside, it is also aimed to impart greater understanding and hence assess the effectiveness of each class of materials in tuning the intrinsic properties of the polymer phase to form a MMM with improved and desired separation performance. The conclusion and future outlook summarize the research activities and present future research directions. 2. Mixed matrix membrane Since the pioneering literature by Zimmerman et al. [23], several signicant review papers on the prospects of MMM as well as the research reports on the capability of MMM as alternative membrane materials for separation processes have been well published [22,2427]. Much research into potential new materials for
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gas separation membranes is driven by the limitation and disadvantages which is in existence in the current available polymeric and inorganic membranes. Few approaches have been carried out to optimize the structure of the polymer chains in order to improve the gas diffusivity by increasing the volume fraction with restrictive or selective channels communicating the voids. In addition to that, attempts have also been made to increase the solubility of permeate molecules by introducing certain chemical afnity for a gas to allow adsorption of certain moieties of the polymer [28]. As the consequences of the efforts made, MMM, a heterogeneous membrane consisting of inorganic ller embedded in a polymer matrix, have emerged as an alternative approach in the stateof-art membrane based separation technology. MMMs are polymer composites that involve phase separated membrane separation system. In this structurally engineered hybrid membrane, inorganic llers act to create preferential permeation pathways for selective permeability while posing a barrier for undesired permeation in order to improve separation performance [29]. The superior permeability and selectivity of inorganic membranes with the processability of polymeric membranes are combined to achieve synergistic separation performance, in which the rigid adsorptive porous type inorganic phase provides superior separation properties and the polymeric phase enables the ideal membrane forming hence solving the problem of fragility inherent found in the inorganic membranes. A wide range of commercialized polymer matrix choices exist within the so-called triangular cross hatched region formed by the upper boundary such as Udel, Matrimid and Ultem have been well known for their practical applications and are readily available for the incorporation of highly selective or permeable dispersed phase to further enhance the current separation performances [23]. The incorporation of llers with molecular sieving properties in the polymer matrix is expected to lead to higher permeability, higher selectivity, or both compared to the polymeric membranes. The incorporation of inorganic llers to the polymer matrix may involve (i) spherical or low aspect ratio llers or (ii) ller thin platelets with very high ratio [30]. The latter case is of recent interest as it offers improved separation properties over the conventional case [14]. Although inorganic llers are used in all cases of preparation, the resulting morphology and membrane separation performance can be varied greatly, primarily arise from different capability of these molecular sieves, either based on shape or size, to discriminate between different molecules present in the feed mixture. Typically, MMMs are easy to process and manufacture as compared with the inorganic membranes. They are normally prepared by casting a solution of polymer and dispersed inorganic phase, and then evaporating the solvent in a controlled environment to obtain a dense membrane. The critical reviews on the recent development and application of MMM have revealed the viability of these materials as an alternative route for the currently existing polymeric and inorganic membranes in industrial applications [22,23,27]. However, new fabrication approach is still in urgent need to reduce materials cost and provide greater permeability for further modications and improvements [31]. The signicant breakthrough on MMM fabrication in useful congurations is undoubtedly essential. Besides that, the comprehensive research on MMM should also be devoted to the successful integration of the inorganic llers to the polymeric phase [32].
3. Inorganic llers as dispersed phase in MMMs The incorporation of inorganic llers into polymer phase can signicantly alter the transport properties of one or several gases through the MMM when compared to that of neat polymeric matrix. The gas transport properties can be enhanced in several ways.
First, the incorporated ller particles could modify the properties of the neighbour polymer phase, which will favor the overall transport properties. This effect is especially signicant for particles that are well distributed within the polymer matrix, where the fractional free volume can be greatly modied [33]. It is also well known that the presence of ller particles may alter the packing, dynamics or conformation of polymer chain near its surface, and impart great effect on the transport of large penetrates relative to small ones. Therefore, the noticeable effect on selectivity of the gas pair involving gases with signicant size difference like CO2/He can be observed. Apart from that, according to Zimmerman and Koros [23], the interface characteristics of the interface between the inorganic particles and the polymer matrix could determine the path to be passed through by one of the gases over the others. This characteristic allows the selective transport of certain gases hence improved selectivity is expected, or in some cases, it can also result in increased permeability by reducing the path length of the permeate molecules. Cages with molecular dimensions open a room for separation to take place, in which the shape and size of these voids can control sorptive selectivity of the favoured permeating species. The best established example of porous materials with these sieving characteristics is the micro-scaled alumino-silicate zeolites and carbon molecular sieve that have been traditionally featured by their intrinsically high separation capacities. In fact, the formation and gas separation properties of MMM using these conventional inorganic llers have been well documented [22,34]. On the other hand, another category of nano-scaled llers, such as silica, CNTs and layered silicate clay are normally featured by intrinsically low separation capacities. Nevertheless, a larger interfacial area between the llers and the polymer matrix per unit volume of the llers can be achieved and have recently attracted considerable attention due to their superior permeation properties [35]. Generally speaking, the variation in the structures and features of these llers may subsequently produce a difference in the separation performance behavior of the resulting MMM. One of the main challenges encountered during the preparation of MMM is to control the chemical structure, surface chemistry as well as the particle types of the inorganic phase that would potentially affect the membrane performance. The preparation of MMM using polymer continuous phase has been reported to be complicated due to the particle agglomeration during solution preparation in which mixing techniques are necessary to break up particle agglomerates prior to the membrane processing. While glassy polymers possess a much attractive separation property relative to rubbery polymers due to their high free volume, the poor polymer chain mobility during the membrane formation may result in a weak interaction between the ller particles and the continuous polymer phase. The interaction between the polymer and ller particles is of concern, as the undesirable channels may be created between both phases if the polymer chains do not completely interact with the ller particles. Classication, which is dened as llers separating out from the membrane matrix due to incompatibility and forming separate ller phases or layers during the formation of MMM may deteriorate the gas separation performance of the membranes [36]. Fig. 3 illustrates the void formation at the sieve-matrix interphase. The formation of these non-selective voids at the interface allows bypassing of gases hence deteriorates the selectivity of the MMM [3741]. To overcome this problem, the presence of a bridging agent to facilitate good interfacial interaction is of crucial importance (Fig. 3c). In addition, approaches involving modication of surface hydrophobicity, creating surface roughness as well as the varying of particle composition and pore architecture have also been investigated [38,42]. Another challenge that could be faced during the preparation of MMM is the partial blockage of the ller pore by polymer
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(a)
(b)
(c)
Fig. 3. Interphase properties of MMMs: (a) void formation between the phases and (b) bridging of the ller and polymer matrix upon surface modication.
chains rendering the role of the incorporated ller [43]. In order to minimize the adverse effect and to deal with the abovementioned challenges, the well dispersion and incorporation of the inorganic particles as individuals in the polymer matrix is one of the most important tasks to be addressed. In such circumstance, surface chemistry of the particles may need to be altered using various treatment approaches. 4. Conventional llers Over the past decades, in order to establish MMM with higher gas separation performance relative to the neat polymeric and inorganic membranes, various inorganic materials have been explored and numerous have been identied as potential ller in membrane application. The most heavily researched type inorganic llers are probably zeolite, CMSs and silica nanoparticles which have been traditionally incorporated into the polymer matrix. These llers are known for their versatility from the point of view of chemical composition, particle shape and possibility of chemical adaptation when embedded in polymer matrix. Particularly for zeolite and CMS, the potentials are granted by their dened pore structure that may contribute to enhanced gas selectivity. Preparation of MMM using these conventional llers have received significant attention as they have offered opportunities for advanced separation that transcend upper bound without increasing the energy and processing cost. However, industry applications of these conventional llers in the preparation of MMM is currently at the bottleneck where the simultaneous increase in permeability and selectivity that exceed Robesons trade off boundary is hardly achieved due to the morphological imperfection created in the MMM, in particular the lack of interfacial interaction between the two different phases. To bring the effect of these llers into play, modications through surface treatment are of urgent interest. As mentioned earlier, several detailed reviews on MMM fabricated using these conventional llers have been available. Thus, the following sub-sections will focus on the recent development of MMM using conventional zeolite, CMS and silica, with the emphasis given to the surface modication of these llers. The recent work on modication of the llers and the effects of these modied llers on polymers segmental mobility, packing and interchain interactions as well as the gas transport properties will be discussed. Insight into the evolutions of the recent development of MMM based on these conventional llers offers a clear picture on how the attractive properties of the llers can be further netuned for excellent separation performance. 4.1. Zeolite Zeolites are crystalline, hydrated aluminosilicate with opened three-dimensional framework structures, regular intracrystalline cavities and channels of molecular dimension. Zeolites possess
interesting physical and chemical properties and one of the most remarkable properties, the sorption and diffusion properties of zeolite, are due to the presence of different size channels and cavities that are related to free space or void volume. Since the last few decades, the improvement in MMM performance using zeolite as the dispersed phase has resulted in the commercial alternative over the polymeric and inorganic membrane. The use of zeolite in the formation of MMM as potential ller for gas separation membranes has received numerous attentions due to their thermal stability as well as their promising separation and transport properties. Shape selectivity and specic sorption characteristics of zeolite can be combined with easy processability of polymer to provide desired properties in zeolite lled MMM. Numerous numbers of reports have indicated the favorable effects of employing zeolite as the dispersed phase to improve the permeability and selectivity of various polymers for gas separation of different gas pairs [34,4452]. The gas transport properties of a zeolite-lled MMM rely strongly on the intrinsic properties of the zeolite particles and the dense polymer phase. The expected improvement of incorporating zeolite in the polymer matrix is gained from suspended zeolite particles that are incorporated into the dense polymer matrix. These particles are selective for one permeate component over another. Thus, the undesired components typically travel a more tortuous path around the zeolite particles, thereby decreasing mobility for that component and hence resulted in the increase of overall selectivity for the desired species. Early attempts in fabricating MMM using zeolite as dispersed phase focused on the use of common zeolites such as zeolite-A. The proper selection on the type of zeolite is vital to obtain high performance MMM. Previous researches evidenced that the transport properties of MMM is signicantly affected by the type of zeolite used with pore size ranging from 4 to 10 [49,51,53]. This wide range of zeolites can separate gas components either by size discrimination or selective adsorption, depending on the sieving characteristics of the particles. As an example, zeolite 4A, is more favorable for the separation of O2/N2 gas pair than other zeolites due to its appropriate pore size of 3.8 to accurately discriminate between the size and shape differences of spherocylindrical O2 and N2 molecules [23,37]. Fig. 4 depicts the predicted zeolite 4A-PI MMM performance based on Maxwells equation where the shaded boundary represents the commercially attractive region for forming a MMM with thin selective layer. During the early stage of the development of zeolite-MMM, incorporation of zeolite particles into rubbery polymer has shown remarkable progress in the separation performance. The compatibility between inorganic ller and rubbery polymer is good due to the high mobility of the polymeric chains capable to entirely embed the particles [54,55]. Consequently, the promising results exhibited have spurred considerable attention for more research to incorporate zeolite particles into glassy polymer matrix in view of their mechanical stability and more desirable transport proper-
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Fig. 4. Predicted zeolite 4A-PI MMM performance based on Maxwells equation. The shaded boundary represents the commercially attractive region for forming a MMM with thin selective layer [37].
Fig. 5. Sieve-in-cage SEM morphology exhibited by zeolite particles when incorporated in polymer matrix [47].
ties relative to rubber polymer [51]. In the preparation of MMM, a key factor is represented by the afnity between the two phases involved in the nal structure. However, unlike the good contact between rubbery polymers and zeolites at their interfaces, initial attempts at fabricating MMM using glassy polymers and zeolites have resulted in the presence of voids between the polymer and zeolite. Poor adhesion at the zeolite-polymer interface can result in sieve-in-a-cage morphology that is responsible for the nonselective penetration of gas molecules as depicted in Fig. 5 [47], hence reduce the apparent selectivity of the mixed matrix membrane and increase the permeability. While the research during the past few decades focused intensively on choosing an appropriate molecular sieve with dimensions capable of discriminating two penetrating gases with precisely similar dimension, the recent development of zeolite/MMM is looking for effective solution to re-
solve the poor adhesion problem as mentioned above. A wide range of modication involving the surface chemistry of zeolite llers in the formation of MMM has been introduced to allow enhancement in polymer-ller interaction, thus optimization of the transport and separation properties. The early attempts were made through the coating of a diluted solution of a highly permeable silicone rubber on the membrane and later on, efforts to eliminate these unselective gaps often focused on the use of a coupling agent, which is normally a low molecular weight compound with multifunctional groups, to introduce favorable interactions between the polymer and zeolite. Low molecular weight organic compound such as TAP has been used as the tertiary component to link the polymer chain to the zeolite crystal hence promote better adhesion at the interface. Alternatively, the chain characteristics of the polymer matrix can be modied using low molecular weight additive that lead to antiplasticization of polymer matrix [34]. Long aliphatic and polyaromatic based compounds containing polar atoms, rigid and planar structure are usually used to increase the stiffness of the polymer matrix due to reduced rate of segmental motions in the polymer chains which normally resulted in an increased selectivity accompanied with decreased gas permeabilities [56,57]. Surface modication of zeolite using silanes that enables chemical link between zeolite particles and the polymer matrix is also proven to be an effective approach to improve both interfacial adhesion and gas selectivity of the MMM by modifying the surface properties of zeolite from hydrophilic to hydrophobic as well as increasing zeolite afnity to the functional groups of the polymer matrix [5860]. However, the presence of common silane agent such as aminopropyltriethoxysilane (APTES) or 3-aminopropyltrimethoxysilane (APTMS) induces huge number of coupling point on the zeolite surface which may result in pore blockage. In such circumstances, the use of alternative silane agent such as APDMS could be solution to reduce the number to coupling point hence avoid major blockage of the zeolite pores [58]. Another way that has been reported to eliminate the voids and solve the interfacial problem is by adding a plasticizer to increase the exibility of the polymer matrix [61,62]. Nevertheless, in some cases, the addition of a plasticizer may lower the intrinsic gas separation performance of polymeric materials. In view of the restrictions arisen from the addition of foreign molecules to the polymer dope, the strategies to create better adhesion have been suggested to carry out by forming a whisker-like structure on the zeolite surface to provide additional roughness for the interlocking between polymer chains and zeolite particles. Table 2 summarizes the recent advances in the surface modication to improve interaction between zeolite llers and polymer matrix [34,52,6368]. While intensive efforts are still on-going to improve interaction with the polymer materials, the recent zeolitic development has also switched to structure and surface engineering to fabricate new kinds of molecular sieve structure with more attractive properties. Hollow zeolite sphere (HZS), a newly developed spherical molecular sieve through layer-by-layer assembling, is of interest as it possesses advantages of zeolite as microporous and crystalline molecular sieve, as well as the properties of spherical ller that would minimize agglomeration and hence improve dispersability and interaction with the polymer phase [6971]. The rst intention of using HZS as inorganic ller in MMMs for gas separation has been reported by Zornoza et al. [69], showing that the separation performance of gas mixtures H2/CH4, CO2/N2 and O2/N2 was significantly improved due to the spherical shape that has contributed to good dispersion and well ller-polymer contact as well as the hollow nature to allow fast ow and increase the gas permeability. The author also pointed out that, the improvement in the permeability was not only attributed by the free volume through the disruption of the polymer chains, but also related to the hollow space
P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264 Table 2 Recent advances in zeolite/MMMs. MMM composition Polymer Poly(RTIL) PES PSf PDMC PES PEEK PC PMMA Filler SAPO-34 SAPO-34 Zeolite 3A SSZ-13 Zeolite 4A Zeolite NaA Zeolite 4A Zeolite 4A Coupling agent/Silane agent/additive RTIL [emim][Tf2N] HMA APTMS APDMES Dynasylan Ameo DEA p-NA TMOPMA Gas pair Separation performance With modication CO2/CH4 H2/CH4 H2/CO2 H2/CO2 CO2/CH4 CO2/CH4 O2/N2 O2/N2 H2/CH4 CO2/CH4 O2/N2 Without modication
249
Reference
a = 24.9, PCO2 686 Barrer a = 175.8, PH2 7:1 Barrer a = 4.64, PH2 7:06 Barrer a = 2.4, PH2 14:3 GPU a = 41.9, PCO2 88:6 Barrer a = 28.7, PCO2 6:7 Barrer a = 2.7, PO2 4:3 Barrer a = 4.2, PN2 0:12 Barrer a = 135.0, PH2 13:4 Barrer a = 51.8, PH2 4:6 Barrer a = 5.4, PO2 0:86 Barrer
a = 61, PH2 0:206 Barrer a = 2.45, PH2 12:57 Barrer a = 1.7, PH2 82 GPU
[63] [64] [65] [66] [67] [52] [34] [68]
a = 2.9, PCO2 33:8 Barrer a = 2.1, PO2 9:0 Barrer a = 4.2, PN2 0:16 Barrer a = 54.4, PH2 13:4 Barrer a = 32.5, PH2 7:8 Barrer a = 5.1, PO2 2:4 Barrer
present in each HZS particles in which the molecules that selectively permeate in the hollow particles are allowed to pass through more easily with shorter path, compared to the molecules whose diffusion or adsorption is not favoured by the zeolite llers. Fig. 6 shows the possible route transported by the molecules with different afnity towards zeolite llers [69]. In another recent work, Weng et al. [72] has demonstrated the feasibility of using CMS/ Al2O3 as substrate to improve gas selectivity of MMM. The presence of the substrate has remarkably increased the roughness in the channels with the poly(phenylene oxide) and SBA 15 interface hence resulted in higher permeability of small gases such as H2 and CO2 while interfering the permeability of bigger gases such as N2 and CH4. Momentous improvement of H2/CH4 from 17.6 to 50.9 was observed due to the existence of CMS/Al2O3 substrate to facilitate the aggregation or merging of polymer nodules on the membrane surface that is of great importance to obtain MMM with high selectivity.
4.2. Carbon molecular sieve While zeolites are attracting wide attentions in the fabrication of MMM capitalizing on their size and shape selective capability, the emergence of CMS has also offered an interesting option to be potentially applied as the dispersed phase in MMM. CMS produced from the pyrolysis of polymer, primarily thermosetting polymers, are carbonaceous porous solids that contains relatively wide opening with constricted apertures that approach the molecular dimensions of the diffusing gas molecules [73] and with this manner, they are able to effectively separate the gas molecules with very similar size. Since decades ago, CMS have been evidently proven to be very effective for gas separation in adsorption application due to their superior adsorptivity for some specic gases [74,75]. Thereafter, the interest in developing CMS membranes has been encouraging as a result of the outstanding permeability-selectivity combination compared to that of polymeric membranes [8,27,7679]. The high productivity accompanied with excellent separation properties that exceed the limit of trade-off boundary are mainly due to the porous nature of CMS that have promoted their viability as the selective inorganic phase in the fabrication of MMM. The utilization of CMS particles within polymer matrix is anticipated to offer several advantages over zeolites as the molecular sieve entities. One of the major benets expected from the former combination is that CMS particles appear to have better afnity to glassy polymers, hence allow good adhesion at the interface without introducing processing complexities. Moreover, the separation performances of the CMS can be tailored by modifying the pyrolysis protocol to adapt to a specic gas separation [27].
The typical preparation of CMS/MMM involves the pyrolysis of polymer to obtain the CMS particles, followed by the incorporation of CMS particles in a polymer to form MMM with desired properties. Previously, the initial attempt to incorporate commercial CMS particles into rubbery polymer did not give rise to any or too little improvement on the separation performance, mainly due to the dead-end porous structure of the particles which was inevitably inherent in their manufacturing process [80]. Nonetheless, the later prediction by Zimmerman et al. [23] has provided further insight into the gas transport properties of permeable CMS in MMM. By considering the through porosity in CMS which permits not only sorptive cavities for adsorptive processes but also allows gas permeation, they predicted a promising separation performance of O2/N2 that were well above the upper bound trade-off curve when PM800 particles, obtained from the pyrolysis of PI at 800 C under vacuum, were incorporated in Udel without the presence of defects at the molecular sieve/polymer interface. Due to the enormous potential of CMS, continual efforts to develop and improve the separation performance of CMS in MMM have been undertaken, with an ultimate target of achieving simultaneously high permeability and selectivity while maintaining the superior processibility of typical conventional membrane formation technology [79]. One of the most signicant works corresponding to the incorporation of CMS within polymer matrix to evaluate their possibilities and potential for gas separation has been conducted by Vu and coworkers [8,78]. The CMS incorporated Ultem and Matrimid exhibited profound improvement as much as 45% and 20% for CO2/CH4 and O2/N2 respectively, indicating that the molecular sieving pores and channels of CMS that allow for very high size and shape selectivity have without any doubt been responsible for the remarkable increase in the gas separation performance. Sharing the commonly found limitations during the processing of zeolite/MMM, the rigid nature of the molecular sieve always give rise to the difculty to form continuous and defect free membrane. Another critical issue in the fabrication of CMS/MMM is the attainment of good adhesion between the two phases which is required for effective and optimum transport properties. So far, few approaches have been adopted to solve the interfacial problems between the phases of CMS and polymer. Through the manipulation and control of synthesis method, CMS nanoparticles with well-dened micropores and are readily dispersed in various solvents can be produced [81]. It has also been veried that the occurrence of the sieve-in-cage morphology can be avoided by using CMS in polymer dope with relatively high viscosities [8]. Another viable route to avoid the sieve in cage morphology is though the sizing or priming of the CMS particles with the polymer matrix or sizing agents [8,82]. In fact, the role of sizing agents is still very much debated. Some have considered it as a medium to minimize the aggregation of CMS particles at high loading and promote com-
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Fig. 6. The white arrows represent the faster permeating molecules (H2, CO2 and O2) across 8 wt% HZS-PSF MMMs. While the black arrows represent the molecules i.e. CH4 and N2 with less interaction with hollow zeolites [69].
patibilization of the sieve with the polymer through the formation of more chemical reactive site and surface area to facilitate better adhesion without involving complicated chemical reaction and grafting process, while some claimed that sizing agents are not involve in promoting adhesion but is present to prevent the defects and damage of the particle surfaces [8385]. Razah and Ismail [82] reported the use of PVP K-15 as sizing agent for CMS in the preparation of CMS/Udel MMM to bridge the sieve and matrix by physically inducing the molecular interaction and allow the gas transport through the phases without creating additional nonselective and resistive layer in the interphase region hence improved the O2/N2 selectivity from 3.69 to 6.05. 4.3. Silica Another conventional class of inorganic ller that has received signicant attention throughout the development of MMM is silica nanoparticles which can be further categorized into non-porous silica and ordered mesoporous silica. These llers are in general introduced in the polymeric matrix to form an heterogenous membrane through sol-gel reaction in special conditions in order to develop nanoscale particles of the inorganic oxide in a polymer matrix. In this reaction, the silica precursors are hydrolyzed and condensed into the dispersed nanoparticles in the polymer matrix. Since the dispersion is at the molecular or nano-scale level, the interactions between the silica and the organic part can be tailored in order to manipulate the morphological structure at the interface of the two phases [86,87]. This interesting nding is in contradiction to the Maxwell model prediction of deterioration of the separation performance by the addition of nonporous llers to a polymer matrix due to the loss of polymer volume available for sorption and decrease in diffusitivity attributed to the increased penetrate diffusion pathway length [88,89]. The intensive research in silica/polymer MMM system have shown that the addition of non-porous nanosized fumed silica, which has opposed properties
with porous inorganic llers is of great potential to affect polymer chain packing in glassy and high-free-volume polymers consequently bring about alteration in the gas separation properties. Due to the non-permeability of the nonporous silica particles, the addition of this ller into the polymer matrix does not directly contribute to the change of transport property, but it alters the molecular packing of the polymer chains, resulting in an improvement of the permeation as well as the selectivity [90]. Particularly, the incorporation of nonporous silica into polymer matrix can give rise to two outcomes [91]: (i) increase of polymer free volume without creating non-selective voids which in turn results in increased gas permeation properties and (ii) formation of free volume elements that are large enough to permit non-selective Knudsen transport hence resulting in a decrease in selectivity. The separation performance of silica/polymer system in the early development did not show signicant improvement that transcends Robesons upper bound. In spite of that, stimulating improvement in permeability upon the addition of silica particles within the polymer matrix has been widely reported [9296]. The preliminary investigation of MMM incorporating silica particles, has proposed that the increased gas permeability was the result of the interaction between the residual silanol groups of the silica domain and polar gases such as CO2 hence resulting in improved gas solubility due to the increase of the Henrys law coefcient and the Langmuir sorption constants in the MMM. Additionally, the presence of silica particles have induced the morphology change at the interface resulting in the increased amorphous region of the MMM as well as prompting the increase in the mean distance between the polymer chains through the reduction of the polymer chain packing density at the interface between the two phases. In such case, the polymer structure stiffness ascribed to the increased tortuosity and restricted segmental motion has resulted in higher diffusivity and diffusivity selectivity by disrupting inter-chained packing. An increasing polymer backbone stiffness, also plays a more determining role in the polymer separation performance in comparison with the solubility factor [93,97]. The nature of the interface morphology, corresponding to changes in the free volume concentration, free volume cage size as well as the total frictional free volume of the MMM is strongly inuenced by the type of silica, i.e. methyl phenyl or silanol groups that may interact with the polymer matrix [98]. Besides that, the silica particle loading also signicantly affects the permeability of the gases as at high loading of the nanoparticles and with an increased aggregate size, may also give rise to the nonlinear expansion of the free volume [99]. In spite of very little improvement in terms of the gas selectivity [100], the permeation enhancement upon the addition of silica nanoparticles is still an interesting topic as this characteristic becomes signicant in low-permeable polymers like Matrimid 5218 and polybenzimidazole (PBI) that are susceptible to permeability increasing effect, thus pushes the performance of these polymers to transcend the upper bound. For MMM derived from the incorporation of high loading of silica nanoparticles, the permeation behaviour of the composites depends greatly on the chemical compatibility of the silica particles with the polymer matrix. Recent studies have shown that the weak interaction between the silica particles and polymer matrix may induce void formation during lm fabrication, which has a signicant effect on the physical properties, as well as the gas transport performance of the hybrid membrane [88,101104]. Paul and Takahashi [101] revealed that dispersion of fumed silica nanoparticles into PEI has resulted in small but very inuential voids or defects formation at silica/polymer interface or within the aggregates. However, by controlling the interaction between these two phases, the amount of voids at the interface can be controlled and the presence of extra voids volume is believed to contribute to improved gas permeability. Therefore, the reduction in selectivity
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Fig. 8. The transport properties i.e. (a) permeability and (b) permselectivity of the gases through neat PBI and PBI silica hybrid membranes versus weight fraction of silica in the polymer [87].
regardless of gas pair indicated the voids created a parallel pathway through the polymer matrix, as illustrated in Fig. 7, hence allowing unselective transport of all gases when considering that there is no effect of the nanoparticles on the local matrix properties. In the consecutive study where the silica particles were chemically modied with silane coupling agent with unique bifunctional groups to create greater compatibility with the polymer matrix, they reported the reduction of the gas permeability for all gases due to the elimination of parts of the void contents [105107]. It has been suggested that by using a coupling agent, the hydroxyl groups on the surface of the silica particles could be replaced by the organofunctional groups of the coupling agent, hence facilitate better reaction with the polymer chains [108]. While the exploratory research on silica/polymer MMM emphasized the ability of this hybrid system in boosting the gas permeability and justied the suitability of silica particles in highly selective but low permeability polymeric membrane to result in gas separation performance that surpasses the trade off curve, recent investigations have focused on the efforts to improve both
Fig. 7. The possible distribution of spherical silica llers in MMMs that are partially fused together (a) dispersed ller and voids and (b) agglomerated ller and voids [101].
permeability and selectivity in order to make this material more attractive for industry applications. Sadeghi et al. reported a simultaneous enhancement in all gas permeability and as much as 20 times increase in CO2/N2 and CO2/CH4 gas selectivity in MMM prepared by incorporating high loading of silica nanoparticles within ethylene vinyl acetate (EVA) [109] and PBI [87] via solgel method. Fig. 8 shows the transport properties of gases through neat PBI and PBI-silica MMM. The relative high content of silica accompanied by the increased number of active OH group sites has given rise to an increase in solubility and a corresponding decrease in the diffusivity of the gases through the MMMs that eventually resulted in the enhanced gas solution of condensable CO2 gases in the polymer matrix and reduction in the permeability of the non-condensable N2 gas, hence changing the dominant gas permeation mechanism from the diffusion to the solution diffusion. The authors also pointed out that, the reduced diffusivity of the gases can be related to the restricted motion of the gas molecules in the polymer phase and formation of pathways with more tortuosity in the polymer upon the addition of silica particles. Very recently, Xing and Ho [110] have investigated the separation performance of MMM prepared by incorporating fumed silica into crosslinked polyvinylalcoholpolysiloxane. The addition of silica particles has resulted in signicant effect on the separation performance in which the silica content is the most inuential factor to manifest simultaneously high CO2 permeability and CO2/H2 selectivity, which can be attributed to the decrease of H2 transport within the MMM as the packing density of nonporous silica increased. Ordered mesoporous silica with variety of particles size, shape and pore diameter is another form of silica that has been potentially used for the development of new generation of MMM. Prior to their employment in MMM, these mesoporous materials have already received worldwide attention as viable absorbent and membranes in many applications [111,112]. Two of the most common members, MCM-41 and MCM 48 are distinguished from their pore structure in which the former has a one-dimensional pore channel structure while the latter possesses three-dimensional interconnected cubic pore structure. Since the discovery of their favorable effects of increasing the permeability of MMM without decreasing its selectivity due to its good compatibility with the polymer matrix [38], the potential application of these ordered mesoporous materials have been expanded as inorganic ller in the fabrication of MMM. Unlike the role of other size selective molecular sieves, the incorporation of these mesoporous materials in MMM may result in a selective membrane through the improvement of the ller-polymer interaction [113]. Since the cross sectional areas per chain of the most selective synthetic polymer are
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around 1 nm2 or less and considering the typical ordered mesoporous silica has relative large pores ranging from 2 to 50 nm, the polymer chains are able to penetrate into the mesoporosity of the ller to give rise to a real homogenous nanoporous composite, hence render the good adhesion between the llers and polymer matrix. Another interesting feature of these ordered mesoporous silicas when incorporated in polymer matrix is mainly due to the large surface area with abundant reactive silanol groups, which can bridge the polymer chains through hydrogen bonding. The increase in gas permeability as compared to those in neat PSF was observed for MCM-48/PSF [114] and MCM-41 /PSF [115] MMM by Kim et. al. The double increase in permeability of the MMM was associated to an increase in diffusivity as well as solubility. When the loading of mesoporous silica in the polymer matrix is high enough to lead to the formation of a connected silica inorganic phase, the transport properties of the composite can be ruled by the inorganic phase [116]. The increase in diffusivity can be accounted to the presence of high diffusivity tunnels and redistribution of the rigid polymer chains near the pore entrance. The continuous pathways present in the polymer matrix incorporated with MCM-48 as well as MCM-41 silica have allowed the diffusion of gas molecules solely through the molecular sieve phase. The concurrent increase of the gas solubility was attributed to the high coverage of silanol groups on the silica surface that has resulted in higher adsorption capacity of the mesoporous silica relative to that of PSF. However, studies also revealed that the hydrogen-bonding interactions between the surface silanol groups on the surfaces of the mesoporous silica and the aryl ether groups of PSF can be detrimental to the permeability of gases as the silanol groups may cause blockage near the pore entrance, leaving the inner pores inaccessible [38]. Moreover, this material suffers from some limitations concerning gas separation performance as the gas transport can be dictated by the inorganic mesoporous and the mechanism commonly follows the Knudsen diffusion model where the silica llers has higher permeability than the polymer phase. Recently, Zornoza et al. [94,113] investigated the spherical mesoporous MCM-41 with 24 lm pore size by taking advantage of the narrow size distribution that facilitate the formation of homogeneous MMM through the minimization of agglomeration of the silica particles. Increase in both permeability and selectivity for H2/CH4 and CO2/N2 at optimized loading of 8 wt% has been reported, due to the bimodal pore distribution that favors the gas diffusivity as well as the disruption of polymer chain packing and linking due to the presence of silica llers. The results displayed
in Fig. 9 indicates that with the optimum loading and testing condition (temperature and pressure), the relationship between permeability and selectivity for the mixture are located within the Robeson upper bound region. The study also revealed that the different approach use for the removal of structural agent from the bimodal pores of the ordered mesoporous silica spheres has an affecting role in the separation performance where the selectivity of chemically extracted mesoporous silica was slightly lower than that of the calcined ones, while exhibiting relatively higher permeability. The authors concluded that these chemically extracted mesoporous silica spheres could be an energetically cheaper alternative for the fabrication of silica/MMM [94]. 4.4. Metal oxide The preparation of MMM using impermeable particles has been dominated by the use of fumed silica as the dispersed phase. Although some grades of fumed silica contain primary particles as small as 13 nm in diameter, these particles are chemically fused together so that it is not possible to disperse the primary particles individually or in nanoscale aggregates. Metal oxide nanoparticles such as MgO and TiO2 are emerging materials due to their potential applications for membrane-based separation purposes. The primary particles with diameter in nano-scale and high specic area of these metal oxides allow improvement in particle distribution and prevent non-selective void formation in nanoparticles/polymer matrix interface. Therefore, these nanoparticles are not inherently fused together and have potential to be dispersed individually or in nanoscale aggregates. The incorporation of metal oxides normally exerts similar effect as that of impermeable silica particles in which the alteration of gas transport behaviour in such MMM is the result of chain packing disruption and nanoscale agglomeration of nanoparticle in polymer matrix. It is in common consent that, the incorporation of metal oxide nanoparticles in the optimum condition would result in signicantly improved permeability while maintaining selectivity or in certain cases, diminishing the overall diffusivity selectivity of the MMM due to the inability of the porous structure of nanoparticles to selectively distinguish the gas molecules based on their size difference. Several research work related to MgO embedded in MMM have been reported [117119]. According to Hosseini et al. [117], the enhanced gas permeability was ascribed to the effect of nanoparticles on the gas diffusivity due to the incorporation of highly porous MgO nanoparticles which have substituted some portions of the dense structure of polymer chains in the membrane struc-
Fig. 9. Results for (a) H2/CH4 and (b) CO2/N2 at different pressures and temperatures for mesoporous silica sphere incorporated into Matrimid and Udel [94].
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ture. The increase in permeability was also seen to be the result of the presence of microvoids at the polymerparticle interface as well as the inherent transport properties of porous particles MgO nanoparticles that encompass pore size that is larger than the kinetic diameter of gases in which all the gas molecules, regardless of size, can pass through the particles without any resistance against their transport. In principle, the presence of afnity and interaction between MgO surface and some gas species, CO2 for example, has also prompted the enhancement in the transport of the molecules. For instance, Matheucci [119] reported that CO2 permeability increased from 52 barrer in the neat poly(butadiene) to 650 barrer in MMM containing 27 vol% (nominal) MgO, ascribed to the surface properties of MgO nanoparticles that are basic in nature also show high afnity of physisorption towards acidic CO2 molecules hence adsorbed large concentration of CO2 even at low pressure and consequently enhanced the gas permeability. Matteucci et al. have conducted systematic study to investigate the inuence of TiO2 particle surface chemistry on the gas transport properties of the MMM based on both glassy [120] and rubbery polymer [121]. Upon the incorporation of TiO2 into the polymer matrix, the dispersion of these nanoparticles was varied depending on the amount of loading. The MMMs were presumed to be defect free at low particle loading in which the nanoparticles were dispersed individually and in nanoscale aggregates whereas when high loading of TiO2 were lled into the polymer, some nanoparticles formed micron-sized aggregates, indicating the presence of transmembrane defects at such high ller concentration. Besides demonstrating great inuence on the dispersion properties, the loading of TiO2 was also found to manipulate the gas transport properties of the MMMs. The diffusivity selectivity of gas pairs consisted of CO2 and nonpolar gas appeared to increase with increasing particle loading. Similar trend was observed in a recent study performed by Moghadam et al. on the effect of TiO2 when embedded in glassy polymer [122]. The void formation in nanoparticles polymer matrix interface as well as agglomeration of particles and weak interaction between polymernanoparticles at interface, particularly at high loading has led to greater permeability compared to that predicted by Bruggemans model. In general, reduction in MMMs selectivities relative to pure Matrimid has been observed, due to the decrease in diffusivity selectivity. In the case of CO2, the permeability enhancement of Matrimid containing 20 vol% TiO2 was 2.45 times higher than neat Matrimid, while CO2/CH4 selectivity decreased by 33%, revealing that the use of TiO2 nanoparticles improved membrane performance in CO2/CH4 separation yet presented a trade-off line with relatively similar slope with respect to Robeson upper bound. This tendency has arisen from the increase in free volume and voids, which in turn decrease the size-selective nature of the membrane, so that permeability enhancement of large molecules such as nitrogen and methane was more signicant than that of smaller one.
controllable cage dimension is of greater interest as this feature may facilitate better sieving properties to the resulting MMM. Another point of concern is that the external surface modication of the ller particles, particularly with silane coupling agents, has unavoidably give rise to the pore blockage and limit the transport of the gas molecules [39]. Apparently, the developments of MMM using conventional llers are signicant yet inadequate to t the increasing expectation for the practical application in industries. The challenges faced by this MMM have urged extensive researched on the use of other promising alternative materials to help mitigate the existing problems in order to meet the desired membrane separation performance. It is only very recent since attention was driven to this new class of alternative potential llers. Nowadays, the advancement in science and technology has allowed the synthesis of nanomaterials with great control in respect to their composition. While there are still much work devoted to the basic synthesis and characterization of the building blocks, the current challenge seems to transfer the nano-scale properties of these materials into macro-scale structures. The remarkable versatility of these alternative nanostructured llers upon the incorporation in MMM has been recognized as one of the greatest achievements in the area of membrane based gas separation processes as this mixed matrix system has shown tremendous promising separation results. The following sections review and provide further details on how these recently emerging materials, i.e. carbon nanotubes (CNT), clay and metal organic framework (MOF) have offered new and huge opportunities to the development of MMM endowed with attractive and desired characteristics that are comparable or even triumph over the conventional inorganic llers. 5.1. Carbon nanotubes In recent years there have been tremendous research advances made for carbon nanotubes (CNTs) due to their unprecedented physical and chemical properties. The remarkable increase in the number of papers published in the fundamental research as well as in the advanced engineering has indicated the great and unlimited potential of this material to generate huge research activity in most areas of science and engineering. CNTs are a novel and interesting graphitic carbon material that is made up of graphite sheets that have been rolled into a tube. This hollow cylinder, usually capped at least at one end, is considered as nearly one-dimensional structures according to the high length to diameter ratio where the diameter of a nanotube ranges from a few to tens of nanometers, while its length can reach up to several millimeters. Generally, as depicted in Fig. 10 [123], CNTs can be synthesized as singular tubes known as single walled carbon nanotubes (SWCNTs) or as a series of shells of different diameters spaced around a common axis called multiwalled carbon nanotubes (MWCNTs). Since the discovery of this relatively new class of carbon material, researchers have envisaged by taking advantage of their extraordinary electronic, mechanical, thermal and optical properties that have sparked great interest in their use in a wide spectrum of promising applications. While the research in CNTs is continuing to discern the utility of this nanostructured material, more possible applications are currently being explored and developed. One of the most signicant applications of CNTs is probably as an ideal reinforcing ller in polymer composites that are poised to exhibit exceptional and desired properties through the careful and detailed control of the processing and fabrication parameters. The initial interest of incorporating CNT in polymer lay in the possibility offered by the nanotubes to result in superb mechanical and electrical properties of the fabricated polymer nanocomposites [124129]. In the context of application in polymer composite, MWCNTs are of particular interest over SWCNTs in view of their relatively low cost and avail-
5. Alternative llers Despite the rapid advancement in research focusing on conventional llers that have been traditionally applied in the preparation of MMM, the efforts to create ideal membrane with desired separation properties are still hampered by many undesired and unavoidable obstacles, as identied in the above mentioned studies. For instance, the sieving characteristic of zeolites and CMS is attractive however their size and aspect ratio is less favourable for the production of asymmetric membrane that utilizes a thin permselective layer. Furthermore, the rigid pore size with limited number of possible structure and composition in the conventionally used zeolite and CMS are insufcient to effectively discriminate the gas molecules of similar sizes. A ller material with a
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Fig. 10. (a) Different structures of CNTs and (b) TEM of aligned CNTs [123].
ability in larger quantities as a result of their more advanced stage in commercial production [130]. Since the last decade, considerable research, as summarized in Table 3, has been focused on the incorporation of carbon nanotubes into polymers to prepare MMM [36,131137]. The intensive research conducted are primarily inspired by the theoretical work by Sholl and co-workers [138,139] that have reported about the transport rate of small gases such as H2 and CH4 in close packed bundles of SWCNTs being extremely rapid and in orders of magnitude faster than in zeolite and any other known inorganic nanoporous materials. The pioneering work of incorporating aligned MWCNTs into polymer matrix for transport studies conducted by Hind et al. [140] has provided a clear indication of the potential of the nanotube inner cores to act as a feasible channel for the transport of N2 and proposed the potential application of CNTs in chemical separation and sensing. Several atomic simulation studies have suggested that CNTs can be served as an ideal candidate for gas adsorption and separation purposes as a result of their superior selectivity and permeability for the transport of light gases [141,142]. The exceptional high self and transport diffusivity is attributed to the extraordinary inherent smoothness of the potential-energy surface dened as when the nanotubes are well dispersed in the polymeric matrix and all gas molecules pass through the tube channels resulting in high gas permeability [136]. In the case where the CNTs are vertically aligned to the membrane surface, they would behave like pinholes that allow rapid transport of the gases passing through the channel of the nanotubes, leading to high gas permeability without selectivity [36]. The adsorption selectivity of the gas pair is strongly driven by the interaction potentials of the molecules with the graphitic CNT walls. The difference in the sorption interaction between the permeating gas
Table 3 Recent advanced in CNT/MMMs. Polymer Functionalization/ modication H2SO4/HNO3 H2SO4/HNO3 Ru metal Triton-X100 Chitosan H2SO4/HNO3 HNO3 H2SO4/HNO3 Optimum loading Gas pair
molecules and CNT walls gives rise to improved separation factor of the gas pair in which it has been evidenced theoretically and experimentally that CH4 molecules showed preferential sorption capacity over other gases like H2, O2 and N2, resulting in enhanced gas selectivity [136]. The expected superior separation properties of the CNTs are hard to be realized due to the difculties to assess and achieve morphological defect-free CNT/MMM in real experimental studies. In order to obtain ideal membrane structure in which the spaces between the CNTs are lled with a continuous polymer lm and the closed ends of CNTs are etched opened, the polymer must have high wettability with the nanotubes to allow good interaction between the two phases. Unfortunately, the effort of incorporating CNTs into polymer matrix share the same challenge as other inorganic llers where the poor adhesion of the different phases elicits the presence of an interphase polymer layer near the nanotubes, with properties differing dramatically from the bulk polymer. Apart from the incompatibility of the ller and polymer matrix, the intrinsic properties of CNTs which tend to form stabilized bundles in nature due to the presence of van der Waals force are also a hindrance to the well dispersed nanotubes in the polymer matrix [143,144]. The nature of the dispersion problem for CNTs is rather different from other conventional llers, such as spherical particles and carbon bers, because of the characteristics of CNTs such as small diameter, high aspect ratio and thus extremely large surface area [145]. As a result from the agglomeration and entanglement of CNTs, the defect sites are created hence drastically weakening the effect of CNTs as the ller in the MMM. Correspondingly, to fully utilize the advantages featured by CNTs in a practical manner, the surface modication of CNTs using physical and chemical approaches have been adopted. There are two major issues that need
Separation performance Neat polymer CNT/polymer
Reference
PES PES PEI PI PBNPI BPPOdp PSf
5 wt% MWCNTs 5 wt% MWCNTs 1 wt% MWCNTs 1 wt% MWCNTs 15 wt% MWCNTs 5 wt% MWCNTs 5 wt% SWCNTs 10 wt% SWCNTs
CO2/N2 CO2/N2 O2/N2 CO2/CH4 H2/CH4 CO2/CH4 CO2/N2 CO2/N2 O2/N2 CH4/N2
a = 22.5, PN2 0:12 Barrer a = 21.8, PN2 0:12 Barrer a = 21.8, PN2 0:12 Barrer a = 19.1, PCO2 8:9 Barrer a = 6.7, PH2 4:7 Barrer a = 3.7, PCO2 2:6 Barrer a = 30, PN2 2:6 Barrer a = 5.1, PN2 0:17 Barrer a = 1.0, PCH4 0:17 Barrer
a = 22.5, PN2 0:2 Barrer a = 22.1, PN2 0:20 Barrer a = 26.5, PN2 0:13 Barrer a = 21.8, PN2 0:12 Barrer a = 10.0, PCO2 14:3 Barrer a = 6.7, PH2 8:0 Barrer a = 3.7, PCO2 3:4 Barrer a = 31, PN2 4:7 Barrer a = 30, PN2 2:6 Barrer a = 5.4, PN2 0:23 Barrer a = 1.2, PCO2 0:28 Barrer
[131] [132] [133] [134] [135] [36] [136]
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to be tackled during the surface modication of CNTs prior to the insertion into the polymer matrix. First is to debundle the highly entangled nanotubes to allow improved interfacial interaction and second, the dispersion of the nanotubes to obtain CNTs that are homogeneously distributed within the MMM to facilitate effective gas transport [146]. Aside from the relatively smooth CNT surfaces that render weak interfacial bonding, the nanotubes present large area density of graphitic walls as well as core entrances that can be functionalized by molecules of length, hydrophobicity or chemical functionality, depending on the application of the modied CNTs. Generally, the surface modication of CNTs can be conducted in two manners, i.e. by physical and chemical means. The most conventionally and commonly used functionalized method is through the surface treatment with strong inorganic acids [147149]. During the acid treatment, functional groups such as hydroxyl and carboxyl groups are introduced to the surface of the CNTs to improve their compatibility with the polymer matrix. During the processing, the functionalized CNTs are soluble in a wide range of organic solvents as the hydrophobic nature of CNTs has been altered to hydrophilic due to the attachment of polar functional groups. As the enhancement in gas permeability of MMM is mainly ascribe to the disturbed polymer chain packing by the llers, the intact interaction of the polymer matrix and functionalized CNTs is expected to impart more intimate insertion of the nanotubes into the polymer chains hence more effectively increase the gas permeability [36]. As mentioned earlier, CNTs show high tendency to entangle as ropes or in bundles. Acid treatment has been known as a cutting process to disentangle and disintegrate the nanotubes for better dispersion in polymer matrix, as well as to open up the closed end of the CNTs to facilitate greater diffusitivity of gases molecules [137,150]. Weng et al. [135] studied the effect of high MWCNT loading in PBNBI on the gas separation performance. H2SO4/HNO3 mixed acid treatment resulted in the disintegration of the nanotubes into small fragments that showed high dispersion in the PBNPI matrix, even at high loading of 15 wt%. They observed a maximum increase in the diffusitivities of CO2 and CH4 at 15 wt% MWCNT due to the presence of high diffusitivity tunnels in the CNTs within the polymer matrix as well as the introduction of more free volume of polymer chains into the MMM. This result is in contradiction with the previous observation where the high loading of CNTs may lead to agglomerations and create nanogaps between the two phases in which the polymer chains become discontinuous and the tortuosity around the agglomerated CNTs limits further increase in the gas permeability [36,137]. Apart from contributing to improved interfacial interaction, the presence of functional group from the acid treatment has been proven to interact with the penetrating polar gases to improve the solubility of the gas molecules in the membranes [151]. Very recently, Ge et al. [131,132] reported the increase of CO2/N2 gas selectivity due to the greater afnity of the carboxyl groups on MWCNTs with polar CO2, which can increase
the solubility of the polar gas while hindering that of non polar N2 gas. This feature is of great interest as the higher solubility of CO2 can compensate the selectivity loss caused by the increase of free volume upon the introduction of CNTs. Similar effect has been observed for CNTs that were modied with rubidium metal (Ru) [132]. When the Ru modication site was well controlled and the RU particles were mainly deposited on the external surface of CNTs, greater gas adsorption difference between CO2 and N2 on the outer surface was induced hence altering the solubility and total gas selectivity. It was found that Ru-modied sites can increase diffusion resistance of N2 gas due to the stronger adsorption of the gas molecule on the Ru impregnated external wall, and consequently facilitated the enhancement of the CO2/N2 selectivity. While chemical modication via acid treatment has demonstrated viable route to modify the surface of CNTs, many efforts have been put forward to developing alternative physical approach through non-covalent functionalization to overcome the drawbacks of chemical modication particularly the damage to the CNT structures that may eventually lead to deterioration of the intrinsic properties. The most commonly applied non-covalent functionalization to tailor the interfacial characteristics of CNTs are polymer wrapping and surfactant dispersion. The former approach is achieved through the van der Waals interaction and p p stacking between CNTs and polymer chains containing aromatic rings to form supermolecular complexes of CNTs [134] meanwhile the latter involves the dispersion of CNTs in the presence of surfactants with different charge to exert physical adsorption of the surfactant molecules on the surface of CNTs hence lowers the surface tension to effectively prevent the agglomeration and facilitate the dispersion of CNTs [133]. Aroon et al. [134] developed MMM incorporated with 1 wt% of chitosan wrapped CNTs. A signicant improvement of CO2 and CH4 permeability of 10.47 and 2.26 Barrer, respectively and increase in CO2/CH4 selectivity as much as 51% compared to neat PI were observed. The enhancement of the separation performance was observed due to the wrapping of chitosan molecules around the MWCNTs hence promoting very good segmental bridging of the nanotubes and PI matrix to prevent formation of voids and therefore improved the selectivity. On the other hand, the open-ended chitosan functionalized CNTs acted as tunnels within the polymer matrix to render high gas permeation. Similarly, Sanip et al. [152] employed beta cyclodextrin, a toroid with an inner cavity of several angstroms in diameters, as wrapping polymer to non-covalently functionalize MWCNTs. The attached hydroxyl groups upon the grinding of beta cyclodextrin with the nanotubes played a signicant role towards the enhancement of the CO2 gas permeability by increasing the solubility of the gas molecules through the strong interaction while passing through the channels of CNTs. The proposed transport pathway of the gases through MMMs with different cyclodextrin treated MWCNT loading is depicted in Fig. 11. At high loading, it is found that regardless of the role of cyclodextrin as the dispersing agent, the agglomeration and saturation of CNT particles in the polymer
Fig. 11. Proposed gas transport pathway through MMMs with different loading of MWCNTs: (a) 0.5%, (b) 0.7% and (c) 1.0%. At optimum loading of 0.7%, the oriented CNT channels provided smooth ow and penetration of gas through the polymer matrix [152].
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matrix hindered the fast transport of gases due to increased resistance through the nanotube cavities. Another non-covalent approach of CNT surface modication prior to the incorporation in MMMs has been developed recently through surfactant dispersion [133]. The presence of non-ionic surfactant, Triton X100 on the surface of MWCNTs has reduced the agglomeration hence improved the distribution and dispersion of the nanotubes within the PEI matrix. As such, the Triton X100 treated MWCNT/PEI MMM has exhibited increase in permeance of O2 and N2 as much as 88% and 120% respectively without much sacricing the selectivity. The exploration of CNTs has undoubtedly given a vivid impression on the potential of this nanostructured material as promising ller in MMM. Therefore, CNT/MMM is expected to serve as a valuable mean for upgrading the separation performance of the currently existing polymeric membrane. Presently, research efforts have been actively pursued to utilize the CNTs lled polymer matrix in the eld of membrane separation, particularly in gas separation. The main interest of CNT/polymer system concerns the smoothness of their interior channels that is the main characteristics for the rapid transport of gases within the nanotubes. Despite the viability and merits demonstrated by CNT, one point of concern is that the success implementation of the hybrid matrix still relies vastly on the characteristics of the CNTs as well as the interaction with the polymer matrix. For instance, CNTs as ller has been severely restricted due to the difculties with the dispersion of entangled CNTs during processing and poor interfacial interaction between the nanotubes and polymer matrix. Additionally, it is also noted that the dispersion of the agglomerates is not complete due to a stronger interaction between the primary nanoparticles than with the polymer. The state of the CNTs dispersion in a polymer matrix plays a decisive role for the further application of the MMM. Therefore, a greater understanding of these issues is in wanting to further boost the separation performance to a higher level. Another drawback of CNTs as a nanoller is their higher production cost [153]. Therefore, the mass production of CNT-based functional composite materials becomes very challenging. 5.2. Layered silicate As illustrated in Fig. 12, clay is a naturally occurring layered aluminium silicate that present itself in the form of perfectly crystal-
line aluminium octahedral and silica tetrahedral sheets of one to a few nanometers thick and hundreds to thousands nanometers in extent, depending on the particular layered silicate [154]. The clay mineral, which can be further categorized into ve main groups, namely smectite, illite, kaolinite, chlorite or sepiolite, is a member of the 2:1 phyllosilicates structural family, in which the central octahedral alumina sheet is sandwiched between two tetrahedral silica to form sheets that are piled in parallel to each other and are bonded by local van der Waals and electrostatic forces [155]. The effort of incorporating layered silicates into polymer matrix has been known for few decades stimulated by pronounced improvement in the mechanical, dimensional, thermal, and barrier performance properties, even at very low silicate layer loading [156,157]. One of the attractive properties is the ability of the silicate particles to disperse into individual layers to obtain an aspect ratio as high as 1000 for fully dispersed individual layers, which is hard to be realized in other poorly dispersed particles [156]. It is generally known that layered silicates can exist in two types of structure: tetrahedral-substituted and octahedral-substituted. The polymer matrix can interact more readily with these than with octahedrally-substituted material as for the latter structure, the negative charge is located on the surface of the silicate layers. Montmorillonite, a member of the smectite group, consists of two fused silica tetrahedral sheets sandwiching an edge-shared octahedral sheet of aluminium is probably the most commonly used among the available clay minerals. Depending on the polarity of the ller, the silicate layers can be coupled through relatively weak dipolar and van der Waals forces or in some cases, by strong ionic forces [158]. Montmorillonite is applied in the formation of hybrid membrane due to their attractive properties of relatively high cationic exchange capacity, high aspect ratio and ease of expansion, which could facilitate the intercalation of this material into a wide range of organic species, besides presenting relative competitive low cost and natural abundance [157,159,160]. Along with montmorillonite, hectorite and saponite are the layered silicates that have attracted great attention in the fabrication of nanocomposites [161,162]. Upon the addition of layered silicate ller into the polymer matrix, two idealised and somewhat simplied polymer layered silicate nanoscale morphologies are anticipated: (i) the intercalated structure resulted from one or two extended polymer chains that are inserted into interlayer spaces of the lay-
Fig. 12. Structure of layered silicates [154].
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Fig. 13. Possible layered silicate distribution arising from the interaction of the ller and polymers: (a) phase-separated, (b) interacted and (c) exfoliated [170].
ered clay and (ii) the exfoliated structure in which clay layers are dispersed into the polymer matrix. In both cases, clay llers are able to create a stable layer to the polymer and exhibit unique properties not seen for conventionally lled polymers [163,164]. The resulting unique properties possessed by the layered silicates render the nanocomposites ideal materials for products particularly for high-barrier packaging for food and beverage packaging Generally low oxygen permeability is required for oxygen sensitive food product, while for some food products certain amount of oxygen is required [158,168]. The incorporation of layered silicate into polymer matrix exhibited remarkable molecular barrier properties as a result of the hindered diffusion pathway through the nanocomposite membranes. The studies on gas transport properties of clay/polymer revealed that an appreciable reduction of both diffusion and solubility coefcients are responsible for the permeability reduction of O2 through the membrane, accredited to the tortuous path towards the diffusing gas molecules and the reduced molecular mobility of polymer chains due in the presence of layered silicate ller particles. The aspect ratio of exfoliated silicate platelets also has a critical role in controlling the microstructure of polymerclay nanocomposites and their gas barrier performances [169]. The presence of llers decreases the available free volume in the polymer and the interactions along the clay and polymer matrix interface thus affecting the sorption process of more condensable gases in the polymer membrane which will provide less sorption sites for gas molecules [158]. Fig. 13 depicts the types of mixed matrix that can be obtained when clay is embedded in the polymer matrix. Depending on the interaction between the two phases, three types of composites can be typically obtained, i.e. (i) phase separation, (ii) intercalated and (iii) exfoliated [170]. Recently, a new application for clay minerals as the ller in MMM has been demonstrated. The interesting ndings of separation performance have spurred considerate interest in the systematic transport study of these polymerlayered silicate nanocomposite materials. The easily tailored pore size and compositional variability available of the layered silicate when embedded into polymer network have shed light in applications that span from material development to membrane separations [160]. Defontaine et al. [171] reported a drastic increment up to 145%
for CO2/CH4 selectivity by sacricing the gas permeability compared to the neat PDMS membrane using MMM incorporated with Sepiolite clay minerals. Sepeolite, a layered silicate with tunnellike structure of approximately 3.710.6 cavity size characterized by the inversion of one every six SiOSi bonds in their tetrahedral layer to form interrupted octahedral layers. These layers were found to be covalently embedded in the polymer networks through the formation of SiOSi bonds between the Sepiolite particles and the polymer chains due to the presence of abundant edge silanol groups in the Sepiolite structure thus producing a hybrid polymeric material with inorganic and organic parts. Despite the potential exhibited by these layered silicate material for the application in MMM, layered silicates are usually hydrophilic and their interactions with non-polar polymers are not favourable. As a result, these silicate compounds must be compatibilized with the polymer matrix through various forms of surface modications prior to the incorporation to improve the miscibility of clay with the polymer, thereby achieving good dispersion of clays in the polymer matrix. Another urgent interest for the surface modication is to expand the interlayer space of the clay, in order to allow large polymer molecules to enter into the interlayer space [167]. Modications of the nanolayer surface are generally achieved either by surfactant cation exchange where the hydrated cations within the clay galleries have been replaced by proper cationic surfactants (e.g. alkylammonium) by a cation exchange reaction. The structure and extent of modication are found depending greatly on the type and amount of surfactant used. For instance, the size of the cationic head group of the surfactant, the length and the number of alkyl chains present in the surfactant molecules have been previously reported to play a role in the degree of exfoliation and intercalation [172,173]. However, these determining parameters might be varied from one system to another depending on the type of materials as well as the processing methods, thus unambiguous relationship could not be established among them [174]. One of the leading demonstrations of the gas transport properties of clay/polymer MMM has been conducted on surfactant modied Montmorillonite KSF embedded in polyamide where the increasing amounts of clay ller has induced depletion of O2 and N2 permeability but increase of the O2/N2 selectivity. This is
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possibly due to the barrier properties of the dispersed nanolayer in the polyamide nanocomposite membrane that resulted in a tortuous diffusion pathway for the O2 and N2 [175]. While surfactants have been widely used to render the clay surface hydrophobic, this modication is accompanied with an undesired shortcoming where it generally reduces or impedes delamination of the clay mineral particles into thinner or single layers [176]. Furthermore, it has also been pointed out that only the ionic part of the surfactant could interact in a favorable way with the charged surface of the sheet-like clay particles whereas the long alkyl tail only shows limited compatibility with the polymer chains [177]. As a consequent, the research direction has moved towards seeking for a better compatibilization that is expected interact with the solid particle surface and with the matrix polymer and thus cater for more promising interfacial properties between the phases. The edge modications through the introduction of coupling agent can be accomplished by anion exchange or silane treatment [165,166]. A later study conducted by Hashemifard et al. [178] has demonstrated more interesting CO2/CH4 separation performance for both permeability and selectivity. The incorporation of organic modied montmorillonite, Cloisite 15A into PEI polymer matrix was found to hinder the formation of voids by providing suitable adhesion between the clay ller and polymer matrix. The increased selectivity of 28% relative to the neat PEI exhibited by the clay/MMM was attributed to the high aspect ratio of clay particles combined with the intercalation due to the presence of tallow in Cloisite 15A to render an increase of tortuosity along the gas penetrant path across the dense skin layer. In another study, the authors reported the 0.5% loading of silylated-halloysite nanotubes (HCT) has resulted in the 27% CO2 permeability increment and 8% enhancement in the CO2/CH4 selectivity [179]. Halloysite, a naturally occurring hydrated polymorph of kaolinite with tubular nanostructure, was incorporated into PEI with the aid of N-b-(aminoethyl)-c-aminopropyltrimethoxy silane (AEAPTMS) to facilitate the tubular dispersion throughout the MMMs and enhancing the polymer-ller adhesion. The functionalization of clay minerals with organosilane has been explored as a way to improve clay dispersion in the polymer matrix, thus increasing the intrinsic properties of the resulting clay/polymer nanocomposites. Aside from higher degree of tortuosity that is believed to yield higher selectivity, the increase in selectivity of HNT/ PEI was also ascribed to the presence of silane agent attached to the HNTs in the polymer matrix. Surface modication using silane agents with amine groups is able to effectively enhance the solubility of CO2 solubility which in turn leads to increase in CO2 permeability and selectivity. Therefore, in this study, the selectivity is possibly contributed by the shape or size discrimination passing between the intercalated clay layers. Another attractive layered material that has been recently explored is JDF-L1 sheet particles with promising characteristic for separation of H2 containing gas pair based on selective sieving pores size across the silicate layers [180]. The pore size of approximately 3 has effectively offered a favourable transport for H2 while rendered an important barrier action for CH4, O2 and N2 with relatively larger kinetic diameter (>3 ), particularly when a parallel preferential orientation of the JDF-L1 sheet particles the polymer matrix is expected. Layered silicate clay mineral has been long used as the reinforcing phase due to its easy availability, low cost and more importantly environmentally friendly. However, the application of clay mineral is still new in MMM. The transport properties of clay/polymer MMM have been scarcely reported and only a few scientic publications are available. Therefore, the corresponding knowledge about this process is still incomplete. However, the potential of this material is undeniable and this predestines the clay minerals as promising ller in MMM, which demand a simultaneous improvement in both selectivity and permeability for gas separation.
Remarkably, these primary results have suggested that there lies great potential for further improvement through more feasible structural modication and optimization of the clay mineral. Nevertheless, more research remains to be carried out in order to fully understand the relationship between the clay structures and transport interaction. 5.3. Metal organic framework Metal organic framework (MOF), a hybrid of organic and inorganic porous materials, is essentially coordination polymer formed in the most elementary sense by connecting metal ions with organic linkers to obtain fascinating tuneable pore geometries and exible frameworks that opens a new avenue to be efciently applied in many potential applications [181]. Generally, MOFs are built up of inorganic sub-units in the forms of clusters, chains, layers or three dimensional arrangements that are connected to organic linkers possessing complexing groups such as carboxylates, phosphonates, N-containing compounds by strong ionocovalent or dative bonds [182]. MOFs can be made up from dimers, trimers, tetramers or polyhedral chains in which the linkers are readily modied with various organic groups while maintaining the same structure type in order to preserve the desired properties. Fig. 14 illustrates a few commons MOFs with different structure architectures that could lead to various forms of frameworks and porosity [182]. MOFs are generally classied into rigid and dynamic. The former do not exhibit any exibility behaviour with small changes in volume reecting the content of their pores while the latter displays great exibility and their applications depend not only on the size of the aperture, but also on adsorption conditions. The pores in MOFs have a very uniform distribution and unlike the spherical or slit-shaped pores that are usually observed in zeolites or activated carbons, MOFs incorporate pores with crystallographically welldened shapes including square which may lead to different sieving properties [183186]. Like other porous molecular sieves, the selective gas adsorption in MOFs is achieved mainly based on the following principle mechanisms which are capable of working independently as well as cooperatively in both rigid and exible MOFs: (i) adsorbatesurface interactions that involves the chemical and/or physical interaction between the adsorbent and the adsorbate and (ii) size-exclusion that depends on the dimension and shape of the framework pores [187]. The motivation for incorporating MOFs in MMM could be numerous. Some of the exhibited characteristics are high surface areas which contribute to high sorption capacity, controlled porosity, high afnity for certain gases and high afnity with the polymer chains due to the presence of the organic linkers in MOFs, as well as the high exibility in terms of chemical composition which allow the changes with systematically varying pore size, functionalities and chemical properties of the MOFs through tailored synthesis approaches in order to facilitate the selective binding or adsorption of target gases [188,189]. MOFs with ultra large pores (>1 nm) might allow penetration of polymer chains to facilitate the adhesion of polymer chain to the embedded MOF particles. Molecular dynamics simulations conducted on self-diffusion and transport diffusion of small molecules in MOFs pointed out that diffusivities in MOFs are similar to those in zeolites and the knowledge of molecular diffusivities in MOFs might be used to screen MOFs for use in an identied process [190]. It is found that description based on Knudsen diffusion is insufcient to describe diffusion in MOFs with relative larger pores as the large open volume inside MOFs frameworks are only lled with molecules at very high pressure. Thus, it is more appropriate to conclude that diffusion of molecules in MOFs is dominated by motions where the adsorbed species remain in close contact with the surfaces dened by the pore structure throughout their diffusion.
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Fig. 14. Few commons MOFs with different structure architectures that could lead to various forms of frameworks and porosity: (a) HKUST-1, (b) MOF5, (c) Sodalite-ZMOF and (d) zeolite-rho ZMOF [182].
Aside from the preliminary understanding towards the characteristic and transport behavior of MOFs, the study and the interest for these materials are still at an initial stage and answers are highly desirable for many unanswered questions. One of fundamental challenges to fabricate MOF/polymer MMMs that are technologically attractive is to select appropriate MOF/polymer pairs as well as the MOF that are selective towards certain gases. These criteria appear essential for high performance MMM as there are enormous numbers of MOFs with a broad range of sieving properties that could potentially be used as the dispersed ller phase in a polymer matrix. Keskin and Sholl [191] adopted Maxwell model to predict mixture permeation for CO2/CH4 mixtures in MOF/Matrimid MMM using molecular simulations and mixing theories. The prediction showed that the incorporation of MOF which is either a permeable but unselective MOF like MOF-5 or the high selective one such as Cu(hpbb)(H2hpbb)0.5 can impart very inuential impact on the separation performance of the resulting MOF/MMMs. Specically, for polymer that is very permeable but less selective, identity of high selective MOF as ller is of great importance to obtain a MMM that surpass the trade-off curve for a relevant gas separation. The trend shown in Fig. 15 provides further prediction of different combinations of MOF and polymer that would offer indispensable new knowledge towards the rational identication of the most appropriate MOF/polymer pairs to achieve CO2/CH4 separation with high gas selectivity and permeability. The pioneer attempt of incorporating MOF copper (II) biphenyl dicarboxylate-triethylenediamine as ller in MMMs to facilitate methane transport was reported by Yehia et al. [192] in which the CH4 selectivity has shown encouraging improvement that fur-
ther implied that MOFs can be served as a suitable candidate as the disperse phase for gas separation due to their unique sieving properties. MOF-5, a cubic three-dimensional structure made from Zn4O clusters linked by three 1,4-benzenedicarboxylate molecules have been assembled into thin lm membrane to promote its
Fig. 15. Prediction of different combinations of MOF and polymer to achieve CO2/ CH4 separation with high gas selectivity and permeability [191].
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usage in gas applications and proven to offer unique opportunities with a potential to achieve superior performance [193,194]. Perez et al. [43] studied the gas separation performance of MOF-5/Matrimid and observed increased permeability up to 120% while the ideal selectivity remained constant compared to that of neat polymer at 30% MOF-5 loading. Nevertheless, Matrimid incorporated with MOF-5 has exhibited a remarkable increase in selectivity for CH4 in gas mixture of CO2/CH4 and N2/CH4 due to the coupling effect of favourable MOF-5 afnity towards CH4 and larger solubility of CO2 and N2 in Matrimid. The transport mechanism is not solely based on solubility and diffusitivity in the polymer but also the Knudsen and surface diffusion as facilitated by the MOF-5 porosity as well as by the uniformity of the surface of its wall. Another type of MOF that shows high afnity towards CH4 and favours the permeation of CH4 is Cu-4,40 -bipyridine-hexauorosilicate (Cu-BPYHFS) which is built up from a square network of copper bipyridyl complexes that are pillared by SiF62 ions [195]. Zhang et al. [196] reported a profound increment of CH4/N2 gas mixture selectivity from 0.95 to 1.7 attributed to the high surface area and afnity of Cu-BPY-HFS in the MMM towards CH4 that resulted in the increased solubility and hence selectivity toward CH4. Recently, a new class of MOF with exceptional chemical stability, zeolitic imidazolate framework (ZIF) with tetrahedral network and sodalite cagelike structure that resemble the structure type of zeolite has been identied as an attractive molecular sieve for small gas molecules such as H2 and CO2 [67,182,197]. The addition of ZIF in MMM is suitable to accomplish such purpose as the pore window size of these MOFs can be precisely tuned for a desired gas pair separation. ZIF-8 and ZIF 90, with pore apertures of 3.4 and 3.5 respectively can readily exclude gas molecules with larger size from small H2 and CO2 hence demonstrating promising results in H2/CH4 and CO2/CH4 gas pair separation. In addition, the presence of imidazole linker in these ZIF members is also a contributing factor to the enhanced selectivity as this ligand has been found to favorably interact chemically with CO2 through non-covalent bonding [198]. Bae et al. [188] have reported the performance of ZIF 90/6FDA-DAM MMM that surpassed the trade-off of polymeric membrane performance in which the enhancement in both permeability and selectivity was mainly due to the selective sorption and diffusion of CO2 in the ZIF-90 crystal. In another similar study conducted by Ordonez et. al. [197] using ZIF-8/Matrimid MMM, significant increase in the gas permeability was observed at ZIF-8 loading lower than 50 w/w% due to the presence of MOF llers that has increased the distance between polymer chains and disrupted chain packing in the polymer thus showing an increase in the free volume. A remarkably enhanced selectivity for gas pairs containing small gas molecules was reported at 50% ZIF loading. The increment of 213% and 290% for CO2/CH4 and H2/CH4 respectively was ascribed to the molecular sieving effect of the small pore aperture of ZIF-8 that favors the diffusion of small gas while hindering the easy diffusion of large gas molecules like CH4. As such, ZIFs facilitate the transport of small molecules through the aperture and into the pore, competitive adsorption for gas pair contains both small molecules cannot be realized by these ZIFs. In such circumstances where separation of small molecules like H2/CO2 is desired, ZIF with narrower pore size of about 3 , which is between the kinetic diameter of H2 (2.9 ) and CO2 (3.3 ), is of particular interest as it is expected to show a clear cut-off between these two gases and thus can be served as an attractive ller candidate for MOF based MMMs. Li et al. [67] investigated the potential application of ZIF7 incorporated polyetherimide MMM for H2 separation and noticeably improved separation performance that transcends the tradeoff curve was achieved primarily due to the precise size-selective molecular sieving abilities exhibited by ZIF-7. The gas transport properties of MOF/MMMs have so far been found to be technologically attractive. MOFs are very promising
candidates that stands out for selective gas adsorption, which can lead to gas separation due to its remarkable selectivity and tuneable properties. Furthermore, MOFs can be easily synthesized and variation of MOF compositions and structures including high aspect ratio MOFs is achievable. Organic linkages provide useful platform for chemical reaction to take place that may improve adhesion. Unfavourably, the main constraints of MOF when embedded in polymer matrix are lower thermal and chemical stability due to the presence of the organic linkers. In this aspect, they are still far to compete with traditional llers such as zeolites and CMS. Furthermore, thermal stability of the polymers can be obtained when high temperature is applied to the matrix during solvent removal. These drawbacks must be balanced against the rational design process for tailoring structures to specic properties. However, one should realize that, the true strength of MOF springs directly from the modular process by which they are constructed as they allow greater chemical alteration on a periodic scale, since the methodology for organic transformations is wellestablished [199]. So far, the studies performed have underlined the key role played by the structure of MOFs that are able to offer selective separation based on their sorption capability and pore window size. Such studies have also added further insight into the dependency of the separation performance on the structure architecture in terms of the pore size and rigidity where emphasis can be given during the construction of MOF based MMMs.
6. New and emerging material for MMM 6.1. Graphene Graphene, as new class of carbon nanomaterials, is found to be economical and has novel properties similar to CNTs. Fig. 16 compares the existing low-dimension carbon allotrope i.e. fullerene, CNT and grapheme [200]. Since the early 1940s, the experimental investigation of graphene properties, as a standalone object, has been almost inexistent until recent years due the difculty to identify and univocally characterize the single-atom thick sheet. The direct observations of isolated graphene monolayer recently have sparked an exponentially growing interest in this two-dimensional material. Recent studies showed that graphene could be used as a viable and inexpensive ller substitute for CNTs in nanocomposites owing to the excellent in-plane mechanical, structural, thermal and electrical properties of graphite [201]. Nowadays, graphene and graphene-based nanocomposites are being studied in nearly every eld of science and engineering and possess much importance due to their exceptional electronic and mechanical properties [202 205]. Recent progress has shown that the graphene based materials can have a profound impact on the gas transport. The investigation and tailoring of its transport properties from macroscopic to molecular scales have now captured the attention of many researchers. Graphite can be a good candidate as ller in MMMs due to its high aspect ratio [206,207]. Permeation rate of gas molecules diffusing through membranes can be decreased by embedding high aspect ratio, impermeable particles that provide tortuous paths and reduce the cross sectional area available for permeation [208]. N2 and He permeation through PC lms reinforced with graphite and functionalized graphene sheets (FGS) were studied and the results showed that FGS appears to be slightly better for blocking the diffusion of N2 [209]. On the FGS surfaces, there can be atomistic perforations that CO2 evolution left during pyrolysis treatments, which more likely allow penetration of smaller molecules such as He than larger ones [210]. Furthermore, increased free volume near the graphene-PC interface may selectively expedite transmission of smaller permeants [211]. As such, N2 and He permeability could be reduced by incorporation of graphite and
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Fig. 16. Comparison of carbon allotropes with different dimension: fullerene (0-dimension), CNT (1-dimension) and graphene (2-dimension) [200].
FGS. Interestingly, FGS turns out to be a more effective barrier against diffusing molecules with a larger kinetic diameter implying its potential for materials for gas separation. The use of graphene in different applications is rapidly emerging in current scientic research. Cost effective production of graphene sheets and the potential in gas transport provides a platform for the development of commercially feasible MMMs using this novel material as ller. However, the effective use and experimental demonstration of pure grapheme in MMM for gas separation still remain a challenge. Like CNT and other nanomaterials, the key challenge in synthesis and processing of bulk-quantity graphene sheets is the formation of aggregates that hinder complete and homogeneous dispersion of individual graphene sheets in various solvents. By solving this issue, the new concepts of graphene lled MMMs for desired gas separation can soon be realized. 7. Conclusion and future direction At present, the existing membrane materials are inadequate at fully exploiting new opportunities in the gas separation application. The hybrid system in MMM have the potential to address these requirements by synergistically combining the processing versatility of polymers with the separation characteristics of inorganic molecular sieves and has been the subject of numerous researches. The interplay between basic science and engineering has resulted in some of the most exciting accomplishments in the development of MMM. It is believed that this emerging approach is feasible to attain desired features from both phases and overcome the bottlenecks in each medium. In the last decades, the studies have asserted the unprecedented rapid growth in the eld of MMM. MMM for gas separation are conventionally comprised of zeolite, CMS and silica particles embedded in polymer matrix with the ultimate goal of surpassing the Robeson trade-off boundary by overcoming the drawbacks of the existing organic and inorganic membrane materials. The past decades have witnessed an intense research effort on the application of these llers in various kinds of glassy and rubbery polymeric materials to perform promising gas separation performance. Unlike the transport mechanism in polymeric membranes which is depending largely on the transient intersegmental gaps to effectively separate the gas molecules, inorganic llers
with molecular sieving properties are known to be beneted by the specic pore diameters that fall in between the kinetic diameters of the target gas molecules, resulting in a large diffusive selectivity to the overall selectivity. The typical llers that behave in this attractive manner are zeolites and CMS that have been unsurprisingly granted with tremendous attention since the rst exploration of MMM in the area of membrane based separation. Nonporous silica is a class of impermeable ller that have attracted great interest rooted from their great potential to affect polymer chain packing in polymers to alter the gas separation properties. Metal oxides such as MgO and TiO2 are nanoparticles that have been studied based on their potential to be used as llers in MMM. These nanoparticles normally exhibit high afnity towards certain gas molecules based on their surface interactions, hence wield the advantages of facilitated transport for gas separation through the adoption of appropriate strategy for design and fabrication of the MMM. While the exploration of MMM incorporated with these llers have brought about some forms of delighting breakthrough to be potentially used in separation processes, most of the contemporary studies have concurrently pointed out that there is an obstacle to the successful introduction of inorganic molecular sieve materials into the polymer matrix mainly due to poor compatibility between the llers and polymer matrix, especially when rigid glassy polymer is used as the continuous phase. The interfacial region, which is a transition phase between the polymer and inorganic ller, is of particular importance to crucially determine the separation performance of the MMM. Of importance is the issues related to weak interactions between a glassy polymer matrix and inorganic molecular sieves that may lead to the formation of nonselective voids and resulting in undesired Knudsen ow [39]. Therefore, instead of seeking perfect matching of the inorganic llers and polymer matrix to battle the weakness of MMM in term of adhesion and interaction between the two phases as broadly focused during the early studies, recent efforts have pinpointed the necessity to modify the surface of llers to enhance the interfacial properties. Modication of llers and polymer matrix has become an expanding eld of research and different approaches have been proposed to account for the limitations that originate from the poor interactions between both polymers and llers. Although early studies were mainly focused on the incorporation of conventional inorganic llers, particularly zeolites with
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molecular sieving properties; the research trend in the last ve years has shifted towards the utilization of various potential nanostructured ller particles such as CNTs, MOFs and clay. These newly explored llers have shown to be interesting materials as a competitive alternative for MMM. The need to further explore the development of MMM by using alternative technologies has pushed these nanomaterials to the forefront of applications due to their outstanding gas separation properties. On the other hand, graphene, a one-atom-thick planar sheet of sp2-bonded carbon atoms densely packed in a honeycomb crystal lattice have generated enormous interest for its possible implementation in the preparation of MMM. There is no doubt that graphene has shed some light for a new research dimension in searching for new materials. Even after decades of extensive research, the potential of employing these inorganic llers have not reached the expectation of current gas separation performance. This may be due to several reasons, such as membrane defects and related processing issues, as well as the unfavourable orientation of llers in the MMM. It has become clear that improving the interaction between llers and polymer matrix is the most important criterion towards practical usage of MMM in gas separation. The introduction of functional groups can improve dispersion of llers and change chemical afnities of penetrants in nanocomposite membranes. This enhancement is proposed to originate from the strong interactions between the llers and the polymer matrix. The previous studies have also revealed that, the transport properties in terms of the permeability and selectivity can be further optimized through the detail governing of some inuential key parameters. For this reason, the development of ller materials with controlled properties through various forms of surface functionalization has been a subject of great research challenge to membrane-based separation processes. MMM consist of inorganic llers incorporated into a polymer matrix have the potential to extend or even surpass the separation benets exhibited by the polymeric membrane platform. The unique behaviour found in this hybrid system will allow us to apply it in new and different applications. The membrane technology research community has made great progress in the last decade, yet the currently gained knowledge in respect to the application potential of these llers in the fabrication of MMM may just the tip of the iceberg. Further understanding of the fundamentals of this material, including structure and dynamics, will allow us to produce materials avoiding the trade-offs of conventional systems. The main concern of future research should be dedicated to the utilization of specic molecular interactions to control structure and morphology and prediction from nanostructural data and molecular dynamics simulations. The future of the eld is indeed very bright and breakthroughs in the near future are possible with the continual development of these applications. Through the prediction of the materials properties or maximum theoretical performance for different classes of llers, many new types of llers are expected to emerge as the research topic becomes more and more popular and there are still multitudes of structures waiting to be discovered. Hybrid materials with organicinorganic or bioinorganic character represent not only a new eld of basic research but also, via their remarkable new properties and multifunctional nature, offer great prospects for many new applications in extremely diverse elds.
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Recent Advance of Inorganic Fillers in Mixed Matrix Membrane For Gas Separation

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Separation and Purication Technology 81 (2011) 243264

Contents lists available at SciVerse ScienceDirect

Separation and Purication Technology

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

Dense structure Inorganic fillers

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

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[63] [64] [65] [66] [67] [52] [34] [68]

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

Separation performance Neat polymer CNT/polymer

PES PES PEI PI PBNPI BPPOdp PSf

[131] [132] [133] [134] [135] [36] [136]

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

Fig. 12. Structure of layered silicates [154].

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

P.S. Goh et al. / Separation and Purication Technology 81 (2011) 243264

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