Light absorption due to higher harmonics of molecular vibrations in transparent amorphous polymers for plastic optical fibers

We have studied simple empirical equations to estimate light absorption loss α_v due to harmonics of molecular vibrations of transparent amorphous polymers used in plastic optical fibers (POFs). In the visible region, absorption involves two losses. One is α_v, and the other is the electronic transition absorption loss, α_e. Of the two, α_v is considerably larger than α_e in the wavelength region used for optical communication with POFs. We have clarified relationships between chemical structure of repeat units of polymers and α_v. We find that α_v is proportional to the concentration of specific chemical bonds (C? H, N? H, and Obond;H bonds) in the polymer solid, and we propose empirical equations to estimate α_v from the polymer density and the chemical structure of the repeat unit. These equations are used to estimate α_v of several polymers [i.e., poly(methyl methacrylate), polystyrene, and polycarbonate]. The estimated values are nearly equal to the experimental or reference values. Furthermore, to minimize the attenuation in the POF, we conclude that the POF core polymer should have no N? H, O? H, or aliphatic C? H bonds in its repeat unit.     

New PIM-1 copolymers containing 2,3,6,7-anthracenetetrayl moiety and their use as gas separation membranes

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Synthesis,characterization, and evaluation of novel polyhydantoins as gas separation membranes

Novel polyhydantoins ( PHYs ) were synthesized from original aromatic diisocyanates and bisiminoacetates by a two‐step polycondensation procedure, which involved the cyclization of polyurea intermediates promoted by acid catalysis. The physical properties of the novel PHYs were evaluated by comparing them with a classical PHY derived from 4,4′‐methylenediphenyl diisocyanate. All PHYs were soluble and could be processed into dense films, which showed good mechanical properties (tensile strength up to 110 MPa) and thermal stability of >400 °C. High glass transition temperatures (T_gs), ranging from 260 to 410 °C, were observed. Fractional free volume (FFV) was strongly dependent on the chemical structure, and a linear correlation between gas permeability and FFV of PHYs could be found. The gas separation properties were comparable to those of the commercial polyimide Matrimid^®, with the exception of one of the PHYs which exhibited very promising properties as its gas productivity was comparable to the gas separation performance of well‐established experimental polyimides. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4052–4060     

Fabrication of Matrimid/polyethersulfone dual-layer hollow fiber membranes for gas separation

We have developed almost defect-free Matrimid/polyethersulfone (PES) dual-layer hollow fibers with an ultra-thin outer layer of about 10 × 10⁻⁶ m (10 μm), studied the effects of spinneret and coagulant temperatures and dope flow rates on membrane morphology and separation performance, and highlighted the process similarities and differences between single-layer and dual-layer hollow fiber fabrications. The compositions of the outer and inner layer dopes were 26.2/58.8/15.0 (in wt.%) Matrimid/NMP/methanol and 36/51.2/12.8 (in wt.%) PES/NMP/ethanol, respectively. It is found that 25 °C for both spinneret and coagulant is a better condition, and the fibers thus spun exhibit an O₂/N₂ selectivity of 6.26 which is within the 87% of the intrinsic value and a calculated apparent dense-layer thickness of about 2886 × 10⁻¹⁰ m (2886 Å). These dual-layer membranes also have impressive CO₂/CH₄ selectivity of around 40 in mixed gas tests. The scanning electron microscopy (SEM) studies show that low coagulant temperatures produce dual-layer hollow fibers with an overall thicker thickness and tighter interfacial structure which may result in a higher substructure resistance and decrease the permeance and selectivity simultaneously. The elemental analysis of the interface skins confirms that a faster inter-layer diffusion occurs when the fibers are spun at higher spinneret temperatures. Experimental results also reveal that the separation performance of dual-layer hollow fiber membranes is extremely sensitive to the outer layer dope flow rate, and the inner layer dope flow rate also has some influence. SEM pictures indicate that the macrovoid formation in dual-layer asymmetric hollow fiber membranes is quite similar to that in single-layer ones. It appears that macrovoids observed in this study likely start from local stress imbalance and weak points.     

Polyurethane‐mesoporous silica gas separation membranes

The concept of mixed matrix membrane comprising dispersed inorganic fillers into a polymer media has revealed appealing to tune the gas separation performance. In this work, the membranes were prepared by incorporation of mesoporous silica into polyurethane (PU). Mesoporous silica particles with different pore size and structures, MCM‐41, cubic MCM‐48 and SBA‐16, were synthesized by templating method and functionalized with 3‐aminopropyltriethoxysilane (APTES). High porosity and aminated surface of the mesoporous silica enhance the adhesion of the particles to the PU matrix. The SEM and FTIR results showed strong interactions between the particles and the PU chains. Moreover, the thermal stability of the hybrid PUs improved compared to the pure polymer. Gas transport properties of the membranes were measured for pure CO₂, CH₄, O₂, and N₂ gases at 10 bar and 25°C. The results showed that the gas permeabilities enhanced with increasing in the loading of modified mesoporous silica particles. High porosity and amine‐functionalized particles render opportunities to enhance the gas diffusivity and solubility through the membranes. The enhanced gas transport properties of the mixed matrix membranes reveal the advantages of mesoporous silica to improve the gas permeability (CO₂ permeability up to ~70) without scarifying the gas selectivity (α(CO₂/N₂)~ 30 for 5 wt% SBA‐16 content).     

Adsorbent filled membranes for gas separation. Part 1. Improvement of the gas separation properties of polymeric membranes by incorporation of microporous adsorbents

The effect of the introduction of specific adsorbents on the gas separation properties of polymeric membranes has been studied. For this purpose both carbon molecular sieves and zeolites are considered. The results show that zeolites such as silicate-1, 13X and KY improve to a large extent the separation properties of poorly selective rubbery polymers towards a mixture of carbon dioxide/methane. Some of the filled rubbery polymers achieve intrinsic separation properties comparable to cellulose acetate, polysulfone or polyethersulfone. However, zeolite 5A leads to a decrease in permeability and an unchanged selectivity. This is due to the impermeable character of these particles, i.e. carbon dioxide molecules cannot diffuse through the porous structure under the conditions applied. Using silicate-1 also results in an improvement of the oxygen/nitrogen separation properties which is mainly due to a kinetic effect. Carbon molecular sieves do not improve the separation performances or only to a very small extent. This is caused by a mainly dead-end (not interconnected) porous structure which is inherent to their manufacturing process.     

Recent progress in microporous polymers from thermally rearranged polymers and polymers of intrinsic microporosity for membrane gas separation: Pushing performance limits and revisiting trade-off lines

Polymers are promising materials for gas separation membranes. However, the trade-off relationship between gas permeability and selectivity remains an obstacle for achieving polymer membranes that exhibit high gas permeation with desirable separation efficiency. Improving polymer microporosity is of interest in gas separation membranes to enhance gas transport behavior. Polymer modifications by (a) incorporating intrinsically microporous units and/or (b) increasing chain rigidity can enhance microporosity in conventional polymer membrane materials such as polyimides. These strategies are adopted for new classes of microporous polymers, thermally rearranged (TR) polymers, and polymers with intrinsic microporosity (PIMs), to maximize gas transport properties. Their outstanding gas separation performances have redefined the traditional trade-off lines. This review aims to explore the advances in microporous polymers for gas separation applications. The approaches on TR polymers and PIMs to enhance their microporosity are listed, and their developments are evaluated in the context of revisiting performance limits for industrially relevant gas separation applications.     

Designing aromatic polyamides and polyimides for gas separation membranes

Aromatic polyamides and polyimides with improved gas permselectivity, can be designed and prepared by systematically changing structural elements that affect these properties. Indeed, a conscientious choosing of the chemical changes may still provide a promising approach to get better and better polymers for selective filtration of gases. The results of this work, in which novel monomers have been used, have confirmed that gas permeability through aromatic polyamides and polyimides much higher than that of conventional polyamides and polyimides can be achieved. It has been done by introducing bulky side groups, using non-planar monomers, and combining these elements on both monomers: diamines and dianhydrides or diamines and diacids. A theoretical study has also been made to explain the behaviour of some individual polymers, comparing experimental and calculated values of density and free volume.     

Progress in low‐loss and high‐bandwidth plastic optical fibers

Plastic optical fibers (POFs) are highly promising transmission media for future home networking.In comparison to glass optical fibers (GOFs), which are commonly used in core and metropolitan networks, POFs offer many advantages such as great flexibility and easy handling. This review begins with the basic concepts of optical fibers and moves on to the early history of loss reduction in POFs. What drastically changed the status of POFs in the communications field was a graded‐index technology that improved the bandwidth to over 1 gigabits per second. However, even after the loss and bandwidth were enhanced to their limits, the performances of POFs were insufficient for market demand when using conventional optical polymer materials such as poly(methyl methacrylate). Recently, this problem has been solved by several lines of material research using fluorinated polymers. As a result, high‐speed optical home networking by POFs has become more realistic. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Formation and thermal stability of BMI-based interpenetrating polymers for gas separation membranes

Semi-interpenetrating polymer networks (semi-IPNs) were prepared by sol–gel technique through in situ polymerization of bismaleimide (BMI) in thermoplastic polyetherimide (PEI) as well as in polysulfone (PSF). This synthesis route allows arresting thermoset/thermoplastic phase separation at an early stage by solidifying the semi-IPNs through membrane phase inversion. The phase separation could be observed visually in the casting solution or by optical microscope on the surface of the produced membranes. These semi-IPNs with a density lower than their thermoplastic base polymer allowed easier water penetration during membrane phase inversion. This led to improved membrane morphology that was confirmed by scanning electron microscopy. Membranes fabricated from these semi-IPN materials had thinner skin layers and longer straight fingers perpendicular to membrane surface. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that these semi-IPNs membranes have improved glass transition temperatures but a lower thermal stability. However, at ambient conditions, these membranes with their improved structure and morphology showed superior gas separation characteristics compared to base polymers. For example, the permeance was increased by 12–15 times without a significant decrease in the selectivity of oxygen over nitrogen in air separation experiments.     

Evaluation of a mathematical model using experimental data and artificial neural network for prediction of gas separation

In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming＇s study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network （ANN） technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network     

New soluble polyamides with high transparence and improved gas separation properties

Abstract

Based on the aromatic diamine monomer containing di-tert-butylbenzene and methyl groups, this work proposes its polymerization with four different dicarboxylic acids. The prepared polyamides (PA 3a–3d) were characterized by GPC, FTIR, ¹H NMR, mechanical, thermal, optical and gas separated techniques. They exhibited high solubility and good optical transparency. Their optical transmittance at 450?nm wavelength was in the range of 81.4%–86.8%, and the cutoff wavelength was in the range of 327–352?nm. The membranes also had good mechanical properties with tensile strength of 79.7–91.4?MPa, elongations at breaks of 9.0–10.9% and initial modulus of 1.5–1.9?GPa. Meanwhile, these membranes possessed good thermal properties with glass transition temperature (T _g) values of 226–246?°C. The permeability of CH₄, N₂, and CO₂ for these membranes was tested by constant pressure-variable volume method. The PA 3d containing tert-butyl moiety in the diacid units exhibited highest permeability (P_CO2 = 31.4 and P_N2 = 1.9) whereas PA 3c containing hexafluoroisopropylidene moiety exhibited highest selectivity (CO₂/CH₄ = 22.2).     

Design,synthesis, and characterization of a partially chlorinated acrylic copolymer for low‐loss and thermally stable graded index plastic optical fibers

As a novel material of low loss and high thermal stability, a graded index plastic optical fiber (GI POF) comprised of a copolymer of methyl α‐chloro acrylate (MCA) and 2,2,2‐trichloroethyl methacrylate (TCEMA) was prepared and the thermal, mechanical, and optical characteristics were investigated. Although each homopolymer had low loss and desirable high thermal stability, they had crucial disadvantages for the fiber fabrication process. To draw a MCA polymer (PMCA) fiber, it has to be heated above 270 °C. However, the polymer started to decompose at a lower temperature and produced numerous bubbles. In contrast, TCEMA polymer (PTCEMA) is too brittle to roll up during heat drawing. In this study, we succeeded to improve the strong viscoelasticity and the low decomposition temperature of PMCA and the brittleness of PTCEMA by copolymerizing MCA and TCEMA. In addition, the glass transition temperatures (T_g) of the copolymers were in the range of 133–147 °C and the transmittances of the copolymers were much higher than that of PMMA which has been commonly used as a base material of POF. A suitable GI POF was obtained using the MCA and TCEMA copolymer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3352–3361, 2009     

Cobalt-doped silica membranes for gas separation

Cobalt-doped silica membranes were synthesized using tetraethyl orthosilicate-derived sol mixed with cobalt nitrate hexahydrate. The cobalt-doped silica structural characterization showed the formation of crystalline Co₃O₄ and silanol groups upon calcination. The metal oxide phase was sequentially reduced at high temperature in rich hydrogen atmosphere resulting in the production of high quality membranes. The cobalt concentration was almost constant throughout the film depth, though the silica to cobalt ratio changed from 33:1 at the surface to 7:1 at the interface with the alumina layer. It is possible that cobalt has more affinity to alumina, thus forming CoOAl₂O₃. The He/N₂ selectivities reached 350 and 570 at 160 °C for dry and 100 °C wet gas testing, respectively. Subsequent exposure to water vapour, the membranes was regenerated under dry gas condition and He/N₂ selectivities significantly improved to 1100. The permeation of gases generally followed a temperature dependency flux or activated transport, with best helium permeation and activation energy results of 9.5 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ and 15 kJ mol⁻¹. Exposure of the membranes to water vapour led to a reduction in the permeation of nitrogen, attributed to water adsorption and structural changes of the silica matrix. However, the overall integrity of the cobalt-doped silica membrane was retained, given an indication that cobalt was able to counteract to some extent the effect of water on the silica matrix. These results show the potential for metal doping to create membranes suited for industrial gas separation.     

Superior gas separation performance of dual-layer hollow fiber membranes with an ultrathin dense-selective layer

A concept demonstration has been made to simultaneously enhance both O₂ and CO₂ gas permeance and O₂/N₂ and CO₂/CH₄ selectivity via intelligently decoupling the effects of elongational and shear rates on dense-selective layer and optimizing spinning conditions in dual-layer hollow fiber fabrication. The dual-layer polyethersulfone hollow fiber membranes developed in this work exhibit an O₂/N₂ selectivity of 6.96 and an O₂ permeance of 4.79 GPU which corresponds to an ultrathin dense-selective layer of 918 Å at room temperature. These hollow fibers also show an impressive CO₂/CH₄ selectivity of 49.8 in the mixed gas system considering the intrinsic value of only 32 for polyethersulfone dense films. To our best knowledge, this is the first time to achieve such a high CO₂/CH₄ selectivity without incorporating any material modification. The above gas separation performance demonstrates that the optimization of dual-layer spinning conditions with balanced elongational and shear rates is an effective approach to produce superior hollow fiber membranes for oxygen enrichment and natural gas separation.     

New polyimide-polyaniline hollow fibers: Synthesis, characterization and behavior in gas separation

New polyimide-polyaniline hollow fibers were produced by dissolution of the polymers in NMP and dry/wet spinning of the resulting solution in a non-solvent (H₂O). The morphology and thermal properties of the fibers, were examined by means of SEM and TGA, and FTIR spectroscopy was used for the study of their chemical structure. Permeability and selectivity measurements in different gases (He, H₂, CH₄, CO₂, O₂ and N₂) were performed in order to evaluate the performance of the membrane in gas separation applications. The results indicate that the novel membrane is a well structured hollow fiber, thermally stable up to 500°. The introduction of polyaniline into the polyimide matrix, results in a great enhancement in fiber permeability (60-600 times) possibly due to increase of the total free volume due to the introduction of shorter polyaniline molecules in the matrix, allowing larger quantities of gases to pass through the composite membrane. Perm-selectivity ratios for the composite membranes H₂/CH₄, He/N₂, H₂/N₂ and H₂/CO₂ were found lower by a factor of 6.4, 8.9, 7.7 and 1.47, respectively, compared to membranes produced using only polyimide. The opposite effect was observed for CH₄/CO₂ and N₂/CO₂ perm-selectivity ratios that showed an increase by a factor of 3.52 and 5.2, respectively. The ratio CH₄/CO₂ is of particular interest for natural gas purification purposes.     

Modified cyclodextrin polymers as selective ion carriers for Pb(II) separation across plasticized membranes

In the present work the hydrophobic β-cyclodextrin (β-CD) polymers have been used as macrocyclic ion carriers for separation of Pb(II), Zn(II), and Cu(II) ions from dilute aqueous solutions by transport across polymer inclusion membranes. The β-CD polymers were prepared by cross-linking of β-CD with 2-(1-docosenyl)-succinic anhydride derivatives in anhydrous N,N-dimethylformamide in the presence of NaH. The metal ions were transported from aqueous solutions containing heavy metal ions through plasticizer triacetate membranes with dimer and polymer β-CD derivatives into distilled water. The selectivity of lead(II) over other metal ions in the transport through polymer inclusion membrane was very high, especially for dimer cyclodextrin carrier. In the case of competitive transport of Pb(II), Cu(II), and Zn(II) ions through plasticized immobilized membranes the selectivity of process is controlled via formation of ion pairs of β-CD hydroxyl groups with metal cations. The polymer and dimer of β-CD linked by 2-(1-docosenyl)-derivative used as ionic carriers for competitive transport of metal ions show preferential selectivity order: Pb(II)  Cu(II) > Zn(II). Application of ion carriers mixtures (β-CD polymers and palmitic acid) causes the increase of Pb(II) maximal removal from dilute aqueous solution. The weight-average molecular weight (M_W) and the chemical structure of the β-CD polymers were determined using high-performance size exclusion chromatography with refractive index detector, and ¹H NMR spectroscopy.     

Ni-based amorphous alloy membranes for hydrogen separation at 400 °C

Amorphous alloy membranes composed primarily of Ni and early transition metals (ETMs) are an inexpensive alternative to Pd-based alloy membranes, and these materials are therefore of particular interest for the large-scale production of hydrogen from carbon-based fuels. Catalytic membrane reactors can produce hydrogen directly from coal-derived synthesis gas at 400 °C, by combining a commercial water–gas-shift (WGS) catalyst with a hydrogen-selective membrane. In order to explore the suitability of Ni-based amorphous alloys for this application, the thermal stability and hydrogen permeation characteristics of Ni–ETM amorphous alloy membranes has been examined. A fundamental limitation of these materials is that hydrogen permeability is inversely proportional to the thermal stability of the alloy. Alloy design is therefore a compromise between hydrogen production rate and durability. Amorphous Ni₆₀Nb_40−XZr_X membranes have been tested at 400 °C in pure hydrogen, and in simulated coal-derived gas streams with high steam, CO and CO₂ levels, without severe degradation or corrosion-induced failure. Ni–Nb–Zr amorphous alloys are therefore prospective materials for use in a catalytic membrane reactor for coal-derived syngas.     

Modification for CAAM approach for simulation of binary gas mixture separation in nanometric tubular membranes

In this study a modified solution for CAAM approach, originally presented in our previous work for simulation of binary gas mixture separation in nanometric tubular membranes, is presented by considering the permeate pressure drop along the permeator length. The accuracy of the modified CAAM method is verified by comparing the predicted results with the exact solution, experimental data and the original CAAM method results. Also, a detailed parametric analysis is done to determine the effects of different parameters (feed operational parameters and membrane physical and dimensional characteristics) on the permeate pressure drop along the permeator length.