Membrane inversion method

Phase Inversion (Solution Precipitation). Phase inversion, also known as solution precipitation or polymer precipitation, is the most important asymmetric membrane preparation method. In this process, a clear polymer solution is precipitated into two phases a soHd polymer-rich phase that forms the matrix of the membrane, and a Hquid polymer-poor phase that forms the membrane pores. If precipitation is rapid, the pore-forming Hquid droplets tend to be small and the membranes formed are markedly asymmetric. If precipitation is slow, the pore-forming Hquid droplets tend to agglomerate while the casting solution is stiU fluid, so that the final pores are relatively large and the membrane stmcture is more symmetrical. Polymer precipitation from a solution can be achieved in several ways, such as cooling, solvent evaporation, precipitation by immersion in water, or imbibition of... 

In order to obtain thin skinned, high flux membranes from PVA, several approaches were tried. The method presented in this article is reminiscent of the classical phase inversion method, which is widely applied in casting of asymmetric RO membranes. However, instead of using a gelling bath composed of a nonsolvent... 

In an alternative approach, MIP membranes can be obtained by generating molec-ularly imprinted sites in a non-specific matrix of a synthetic or natural polymer material during polymer solidification. The recognition cavities are formed by the fixation of a polymer conformation adopted upon interaction with the template molecule. Phase inversion methods have used either the evaporation of polymer solvent (dry phase separation) or the precipitation of the pre-synthesised polymer (wet phase inversion process). The major difficulties of this method lay both in the appropriate process conditions allowing the formation of porous materials and recognition sites and in the stability of these sites after template removal due to the lack of chemical cross-linking. 

Today the majority of polymeric porous flat membranes used in microfiltration, ultrafiltration, and dialysis are prepared from a homogenous polymer solution by the wet-phase inversion method [59-66]. This method involves casting of a polymer solution onto an inert support followed by immersion of the support with the cast film into a bath filled with a non-solvent for the polymer. The contact between the solvent and the non-solvent causes the solution to be phase separated. This process involves the use of organic solvents that must be expensively removed from the membrane with posttreatments, since residual solvents can cause potential problems for use in biomedical apphcations (i.e., dialysis). Moreover, long formation times and a limited versatihty (reduced possibUity to modulate cell size and membrane stmcture) characterize this process. 

The spiral wound membranes tested for extraction of impurity-free NaSCN from aqueous process solution were polyamide (PA-300), CTA-700, PERMA-400, and PERMA-250. PA-300 was prepared by interfacial polymerization technique, while the PERMA membranes were prepared by coating a novel proprietary copolymer onto a microporous polysulfone substrate followed by cross-linking of the top layer. Thus, the morphology of these membranes was TFC. CTA-700 was asymmetric in nature and was prepared by solution casting and phase inversion method. 

If 30 is accepted as the lowest reliable number to count and a pour plate method uses a 1.0-ml sample, it follows that the procedures described above are unsuitable for any sample that is expected to contain <30 CFU ml-1, e.g. water samples where the count may be 1 CFU ml-1 or less. Here, membrane filter methods are used in which a large, known volume of sample is passed through the membrane which is placed, without inversion, on the agar surface. Nutrients then diffuse up through the membrane and allow the retained cells to grow into colonies on it just as they would on the agar itself. 

An integrally skinned asymmetric membrane with a porous skin layer (hereafter called substrate membrane) is prepared from a polymer solution by applying the dry-wet phase inversion method and dried according to the method described later, before being dipped into a bath containing a dilute solution of another polymer. When the membrane is taken out of the bath, a thin layer of coating solution is deposited on top of the substrate membrane. The solvent is then removed by evaporation, leaving a thin layer of the latter polymer on top of the substrate membrane. 

Membranes for vapor removal from air have a structure similar to the prism membrane, but they are prepared on a different principle.Aromatic PEI is used to produce a porous substrate membrane by the dry-wet phase inversion method. This polymer was chosen over PS/PES because of the higher durability of PEI to organic vapors. Unlike an asymmetric PS substrate for the prism membrane, the top layer of asymmetric PEI membrane has a large number of pores, the size of which is equivalent to those of UF membranes. When a layer of silicone rubber is coated on the top layer of the porous substrate membrane, the silicone rubber layer will govern the selectivity and the porous support will provide only mechanical strength to the composite membrane. Because the permeabilities of water and organic vapors through the silicone... 

The literature describes numerous manufacturing methods for synthetic membranes. A recent review by Pusch and Walch (1) considers membranes from a number of techniques for manufacturing membranes and discusses applications ranging from microfiltration to desalination to gas separation. In this paper, a thermal phase-separation technique of preparing membranes Is presented. The method Is a development of an Invention described In US Patent 4,247,498 by Anthony J. Castro (,2). This technique Is similar In many respects to the classical phase-inversion methods however, the additional consideration of thermal solubility characteristics of the poly-mer/solvent pair offers new possibilities to membrane production. 

Pore structures of typical polymeric ultrafiltration membranes, produced by so called "phase inversion methods," consist of interconnected, irregular, three-dimensional networks of pores, interstices and voids in their skin layers. 

Selectively permeable membranes can be produced using a molecular imprinting approach. Using a phase inversion method, a poly(acrylonitrile-co-acrylic acid) ultrafiltration membrane was imprinted with theophylline [52], When solutions of theophylline and caffeine were filtered, a significantly greater amount of theophylline was retained within the membrane (Figure 6.33). 

In addition, PEEK-WC membranes have been prepared by using a phase inversion process with supercritical fluids. The supercritical fluid acts as a non-solvent. In comparison to the dry/wet phase inversion method, the supercritical fluid allows the cell size and the membrane morphology to modulate by changing the experimental conditions, such as polymer concentration, temperature, and pressure. A dry membrane can be obtained rapidly and without additional post-treatments. ... 

New cellulose manbranes were recently prepared by the phase inversion method using a green solvent, the ionic liquid [BMIM][C1] [32], After functionalization with a synthetic ligand 2-(3-aminophenol)-6-(4-amino-l-naphthol)-4-chloro-5-triazine, these adsorptive membranes were evaluated for human immunoglobulin G (IgG) adsorption. The authors envisage that a change in the conditions and chemistry for membrane activation with the biomimetic ligand may improve the performance of the affinity cellulose membranes. 

CS is, on the other hand, soluble in acidic solutions and has an excellent film-forming ability. Microporous CS membranes were prepared through phase inversion method and subsequently coupled with various types of ligands to generate... 

The molecular recognition capabilities of polyelectrolyte multilayers have also been investigated by Laschewesky [55], while imprinted films have been grown on membrane surfaces in approaches similar to the phase inversion method for preparing a membrane imprinted with theophylline. Wang et al. [56] adopted an acrylonitri-le/dithiocarbamoyl-methylstyrene copolymer (Fig. 16) to effect separation of caffeine from the theophylline-imprinted membrane. 

Figure 3 Schematic illustration of imprint process of THO in copolymer membrane P(AN-co-AA) by phase inversion method [63,64]. From Ref 46.

Membranes for vapor removal from air have a structure similar to the Prism membrane, but they are prepared on a different principle [22]. Aromatic poly(etherimide) is used to produce a porous substrate membrane by the dry-wet phase inversion method. This polymer was chosen over polysulfone/poly(ether sul-... 

Broadhead and Tresco studied the effects of fabrication conditions on the structures and performances of membranes formed from poly(acrylonitrile-vinylchloride) (PAN-PVC) by using the phase inversion process [85]. They reported the relationship of the fine-surface structure of PAN-PVC membranes to the membrane performance and membrane fabrication method. The fine-surface structure of nodular elements and the size of these elements could be altered by changing the precipitation conditions. Membranes were prepared at 22 on 55 mm diameter polished silicon wafers by spinning at 1500 rpm for 20 s with a spin coater [86]. The film was immediately precipitated in one of the four different precipitation media. The first three media consisted of deionized water at 4,22, and 54 °C. These membranes were referred to as Type 1 , Type 2 , and Type 3 , respectively. The fourth medium was a 50/50 mixture of deionized water and N,iV-dimethylformamide (DMF) at 54 °C and coded as Type 4 . Figure 4.53 shows the histograms of the nodule size distributions observed at the skinned surface of the membranes made under four different precipitation conditions. The sizes of these nodular elements became smaller and more uniform with milder precipitation conditions, which supports the theory that nodules are formed through spinodal decomposition under these conditions. In addition, the size of these nodules could be related to water permeability. Hence, water transport occurred through the interstitial spaces where the pores could be situated. 

Membranes prepared by the dry-wet phase inversion method from glassy polymers are composed of polymeric spheres. 

Separation processes such as ultrafiltration and micro filtration use porous membranes which allow the passage of molecules smaller than the membrane pore size. Ultrafiltration membranes have pore sizes from 0.001 to 0.1 )im while micro filtration membranes have pore sizes in the range of 0.02 to 10 im. The production of these membranes is almost exclusively based on non-solvent inversion method which has two essential steps the polymer is dissolved in a solvent, cast to form a film then the film is exposed to a non-solvent. Two factors determine the quality of the membrane pore size and selectivity. Selectivity is determined by how narrow the distribution of pore size is. In order to obtain membranes with good selectivity, one must control the non-solvent inversion process so that it inverts slowly. If it occurs too fast, it causes the formation of pores of different sizes which will be non-uniformly distributed. This can be prevented either by an introduction of a large number of nuclei, which are uniformly distributed in the polymer membrane or by the use of a solvent combination which regulates the rate of solvent replacement. 

The first breakthrough came in 1959 when Sourirajan and Loeb discovered a method to make a very thin cellulose acetate (CA) membrane using the phase inversion method [4]. This technique produces homogenous membranes with an asymmetric (or anisotropic) structure. The membranes were subsequently found to be skinned when examined under an electron microscope by Riley in 1964 [3]. The membranes consisted of a very thin, porous salt-rejecting barrier of CA, integrally supported by a fine CA porous substrate. Pictures of asymmetric membranes are shown in Figures 1.2 and 1.3. These early Loeb-Sourirajan (L-S) membranes exhibited water fluxes that were lOtimes higher than those observed by Reid, and with comparable salt rejection [5]. The membrane flux was 8—18 1/m /h (knh) with 0.05% NaCl product water from a 5.25% NaCl feedwater... 

Dual layer hollow fiber membranes have become increasingly attractive due to which they can be fabricated in a single step using the non-solvent induced phase inversion method. A good lamination between the two layers as well as a regular morphology are critical to get a functional hollow fiber membrane [80]. 

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