Zeolites compatibility with polymers

The development of a successful zeolite/polymer mixed-matrix membrane with properties superior to the corresponding polymer membrane depends upon good performance match and good compatibility between zeolite and polymer materials, as well as small enough zeolite particle size for membrane manufacturing on a large scale. 

Membrane separators offer the possibility of compact systems that can achieve fuel conversions in excess of equilibrium values by continuously removing the product hydrogen. Many different types of membrane material are available and a choice between them has to be made on the basis of their compatibility with the operational environment, their performance and their cost. Separators may be classified as (i) non-porous membranes, e.g., membranes based on metals, alloys, metal oxides or metal—ceramic composites, and (ii) ordered microporous membranes, e.g., dense silica, zeolites and polymers. For the separation of hot gases, the most promising are ceramic membranes. 

Defect-free membranes comprising zeolites and amorphous glassy perfluoropolymers can be prepared by modifying the surface of the filler. The pure gas permeation experiments of a series of Teflon AF 1600 membranes with various amounts of 80 and 350nm silicalite-1 crystals cannot be interpreted on the basis of the Maxwell model, but are compatible with a model in which a barrier to transport exists on the zeolite surface and a lower density polymer layer surrounds the crystals. With a small zeolite size (80nm) the low density layers around the crystals may coalesce and form percolation paths of lesser resistance and less selectivity. Silicalite-1 crystals improve the CO2/CH4 selectivity of Hyflon AD60X, and drive the N2/CH4 selectivity beyond the Robeson s upper bound. It also turns out that the presence of silicaUte-l crystals, like fumed silica, promote the inversion of the methane/butane selectivity of Teflon AF2400 in mixed gas experiments. 

Most reported zeolite/polymer mixed-matrix membranes, however, have issues of aggregation of the zeolite particles in the polymer matrix and poor adhesion at the interface of zeolite particles and the polymer matrix. These issues resulted in mixed-matrix membranes with poor mechanical and processing properties and poor separation performance. Poor compatibility and poor adhesion between the polymer matrix and the zeolite particles in the mixed-matrix membranes resulted in voids and defects around the zeolite particles that are larger than the micropores of the zeolites. Mixed-matrix membranes with these voids and defects exhibited selectivity similar to or even lower than that of the continuous polymer matrix and could not match that predicted by Maxwell model [59, 60]. 

Most recently, significant research efforts have been focused on materials compatibility and adhesion at the zeoHte/polymer interface of the mixed-matrix membranes in order to achieve enhanced separation property relative to their corresponding polymer membranes. Modification of the surface of the zeolite particles or modification of the polymer chains to improve the interfacial adhesion provide new opportunity for making successful zeolite/polymer mixed-matrix membranes with significantly improved separation performance. 

In an attempt to provide compatibility between the FR and polymer matrix, Wang et al. reported recently on a novel microencapsulated intumescent system containing 4A zeolite as a potential flame retardant for natural rubber (NR).61 The flame-retardant properties of NR composites loaded with different amounts of intumescent flame retardant (IFR), IFR-4A zeolite, and microencapsulated intumescent flame retardant (MIFR)-4A zeolite agents were studied and compared. The LOI data demonstrate that the NR composite filled with 50phr of MIFR-4A zeolite agent and 50phr of IFR-4A zeolite shows better FR properties as compared to NR and 50phr of IFR-filled systems. 

The first known article concerning mixed-matrix membranes was published in 1960 by Barter and James. It examined several different zeolites dispersed in an inert polymer resin to create ion exchange membranes." " Voids were noted at the interface of the two media (i.e., where polymer and sieve meet). These voids resulted in a degradation of mixed-matrix performance. Today, researchers still struggle with material compatibility issues that exist at the solid-polymer interface, as well as other nonideal morphologies introduced by the solid-polymer mixed-matrix technology. ... 

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