Random sulfonated poly(arylene ether sulfone) and sulfonated poly(arylene ether ketone) membranes for fuel cell applications

In this study, sulfonated poly(arylene ether sulfone) (SPAES) and sulfonated poly(arylene ether ketone) (SPAEK) were randomly synthesized, employing a presulfonation process. This presulfonation process resulted in a more controlled and reproducible sulfonation level. The respective polymers were prepared using 2,2-Bis(4-hydroxyphenyl) propane at 50% molar ratio, which also provided some membrane elasticity. The resulting polymers, each had 25% of the block containing the sulfonic domains (SPAES A 25 and SPAEK A 25). Better conductive membranes were achieved for the random sulfone polymers than for the random ketone polymers, with values, respectively, of 0.24 and 0.07 S cm⁻¹ at 80°C. The lower proton conductivity from the ketone-based polymer was compensated with very low methanol permeability (0.25 × 10⁻⁶ cm² s⁻¹) and outstanding oxidative stability. The selectivity of both polymer membranes exceeded the reported values for the state-of-the-art Nafion® 117 and other commercially available options. Both polymer membranes, with their unique combination of ionic domains, elastomeric blocks, and resulting morphology, could be viable candidates for fuel cell applications.     

Thermo‐Responsive Gating Characteristics of Poly(N‐isopropylacrylamide)‐Grafted Membranes

Both hydrophilic Nylon‐6 membranes and hydrophobic poly(vinylidene fluoride) (PVDF) membranes, with a wide range of grafting yields of poly(N‐isopropylacrylamide) (PNIPAM), were prepared using the plasma‐graft pore‐filling polymerization method. The effect of the physical and chemical properties of the substrates on the thermo‐responsive gating characteristics of the PNIPAM‐grafted membranes was investigated experimentally. For both the PVDF and Nylon‐6 membranes, the grafted PNIPAM polymers were found not only on the membranes outer surface, but also on the inner surfaces of the pores throughout the entire thickness of the membrane. The thermo‐responsive gating characteristics of the PNIPAM‐grafted membranes were heavily affected by the physical and chemical properties of the porous membrane substrates. The PNIPAM‐g‐Nylon‐6 membranes exhibited a much larger thermo‐responsive gating coefficient than the PNIPAM‐g‐PVDF membranes. Furthermore, to achieve the largest thermo‐responsive gating coefficient, the corresponding optimum grafting yield of PNIPAM for the PNIPAM‐g‐Nylon‐6 membranes was also larger than that for the PNIPAM‐g‐PVDF membranes.     

Nanoporous poly(methyl methacrylate)-quantum dots nanocomposite fibers toward biomedical applications

In this work, poly(methyl methacrylate) (PMMA)-CdSe/ZnS quantum dots (QDs) nanocomposite fibers were fabricated via a simple electrospinning method. The parameters including concentration of PMMA, feed rate, applied voltage and working distance between the needle tip and the fiber collecting electrode were investigated and optimized to acquire large quantity, uniform and defect-free PMMA and its QD nanocomposite fibers. The surface morphology of the fibers was characterized by scanning electron microscopy (SEM), while the fluorescence emission characteristics of the polymer nanocomposite (PNC) fibers were analyzed with fluorescence microscopy. The thermal properties of the PMMA-QDs PNC fibers were explored by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). In comparison to the pristine PMMA fibers, the PNC fibers with only 0.1 wt% QD loading showed an improved thermal stability by 15 °C for the midpoint and onset degradation temperature. Surface chemical structure and functionalities were probed by a combination of attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). New vibration bands were observed in the PNC fibers in the ATR-FTIR spectra, while the binding energy for both high resolution C 1s and O 1s spectra in the PNC fibers showed an apparent shift toward lower field. Rheological studies revealed a pseudoplastic behavior of both pristine PMMA and PMMA-QDs solutions. Moreover, the formed nanoporous PMMA-QDs fiber media exhibited an excellent biocompatibility as evidenced by the model Chinese hamster ovary (CHO) cell culturing test. The CHO cells demonstrated good adhesion, growth and viability in the reported testing.     

Polymeric hollow fiber membranes for bioartificial organs and tissue engineering applications

Polymeric hollow fiber (HF) membranes are commercially available, i.e. microfiltration and ultrafiltration cartridges or reverse osmosis and gas separation modules, to be applied for separation purposes in industry, for instance to recover valuable raw materials or products, or for the treatment of end‐of‐pipe wastes to avoid environmental impacts, to regenerate or treat waters for reuse and for the separation of key components or clarification in food and beverage industries. They have also shown important benefits as hemodialyzers, hemodiafiltration or plasma purification devices in patients with liver or kidney damage. The good mass transport properties characterizing the polymeric HFs have opened new research areas of application in the biomedical field, such as the tissue engineering (TE) and the construction of bioartificial organs (BAO). In TE, the HFs act as scaffolds or supports and/or allow high permeance of nutrients and waste removal for cell proliferation and differentiation. In BAO, HFs are used for the fabrication of bio‐hybrid constructs that replace the damaged organs of the patient or can be used as in vitro models for therapeutic studies. This review presents the state‐of‐the‐art concerning preparation and application of HFs for TE and BAO and discusses the challenges and future perspectives of the HFs in both fields. © 2014 Society of Chemical Industry     

Use of electrospinning technique for biomedical applications

The electrospinning technique provides non-wovens to the order of few nanometers with large surface areas, ease of functionalisation for various purposes and superior mechanical properties. Also, the possibility of large scale productions combined with the simplicity of the process makes this technique very attractive for many different applications. Biomedical field is one of the important application areas among others utilising the technique of electrospinning like filtration and protective material, electrical and optical applications, sensors, nanofiber reinforced composites etc. Electrospinning assembly can be modified in different ways for combining materials properties with different morphological structures for these applications. The importance of electrospinning, in general, for biomedical applications like tissue engineering drug release, wound dressing, enzyme immobilization etc. is highlighted in this feature article. The focus is also on the types of materials that have been electrospun and the modifications that have been carried out in conventional electrospinning apparatus keeping in view the specific needs for various biomedical applications.     

Low-cost ceramic membranes: A research opportunity for industrial application

Obtaining low-cost ceramic membranes has attracted great interest in the scientific community in last years, as it allows to preserve the advantages of ceramic materials while significantly reduce their manufacturing costs. This type of membranes is mainly based on the use of raw materials and manufacturing processes typical of traditional ceramic materials, i.e silicate-based ceramics. This work exhaustively reviews the raw materials, ceramic compositions and variables of the manufacturing processes used in the development of these membranes, with special emphasis on their numerous potential industrial applications.     

Direct fluorination of polymers—From fundamental research to industrial applications

In this paper fundamental features and industrial applications of the direct fluorination of polymers are reviewed. Direct fluorination of polymers (i.e. treatment of a polymer surface with gaseous fluorine and its mixtures) proceeds at room temperature spontaneously and can be considered as a surface modification process. The author of the current paper and his co-authors have studied the direct fluorination of more than 20 polymers (polystyrene, poly(ethylene terephthalate), poly(2,6-dimethyl-1,4-phenylene oxide), polymethylmethacrylate, low density polyethylene (2 types), high density polyethylene (6 types), polyvinyltrimethylsilane, poly(4-methyl-pentene-1), polyimide Matrimid^® 5216, polysulfones, polyetheretherketone, polycarbonatesiloxane, polysulfone–polybutadiene block-copolymers, polypropylene, polyvinylfluoride (PVF), polyvinylidenefluoride (PVDF), etc.). A large variety of experimental methods, such as FTIR spectroscopy, visible and near UV spectroscopy, Electron Spin Resonance spectroscopy, laser interference spectroscopy, refractometry, electron microscopy, method of surface energy measurement, gas chromatography, method of measurement of permeability of liquids through polymer materials, etc. was applied. Fundamental features of the direct fluorination, such as influence of treatment conditions (composition of the fluorinating mixture, fluorine partial pressure, temperature and fluorination duration) on the rate of formation, chemical composition, density, refraction index and surface energy of the fluorinated layer, kinetics of formation of radicals during fluorination and their termination, texture of fluorinated layer, etc. were studied. On the base of obtained experimental data a theoretical model of the direct fluorination of polymers was developed. It was demonstrated experimentally, that the direct fluorination can be effectively used to enhance commercial properties of polymer articles, such as barrier properties of polymer vessels, bottles and packaging, gas separation properties of polymer membranes and mechanical properties of polymer-based composite materials. Data on a fundamental research and commercial applications provided by other research groups are reviewed.     

Smart composite materials for self-sensing and self-healing

Abstract

The various methods of self-sensing and self-healing developed within the Composite Systems Innovation Centre, University of Sheffield, are reviewed. Damage sensing using electrical resistance in carbon fibre reinforced composite or using the fibres as optical sensing elements in glass fibre reinforced composite is demonstrated. Amelioration of low level damage is demonstrated in both monolithic composite materials and sandwich structures using direct chemical reactions within the matrix without the use of encapsulants. These reactions can be activated by resistive heating of the material itself. The use of a combination of these techniques could create a truly smart structure able to both sense and repair damage and degradation.     

Methacryloxyethyl phosphate‐grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2‐butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGy h^?1), monomer concentration (1–40 %) and solvent were studied and the modified membranes were characterized by weight increase, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C? F (ePTFE membrane) and the C? C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non‐solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. Copyright © 2005 Society of Chemical Industry     

应用基于质谱技术的电子鼻鉴别烟用辅助材料

目的是研究电子鼻系统,利用该系统,基于不同辅助材料挥发物的指纹图,开发出一种简单、快速的鉴别烟用辅助材料的方法。     

Biocomposite membranes of sodium alginate and silk fibroin fibers for biomedical applications

Biocomposite membranes from biodegradable and biocompatible natural polymers were prepared from sodium alginate solution reinforced with silk fibroin fibers in several fiber content by casting and solvent evaporation. The properties of these biocomposites were investigated by scanning electron microscopy, swelling test, water vapor transmission, mechanical and thermal analyses, and cytotoxicity test. A biocomposite with uniform fiber dispersion and good fiber–matrix interaction was obtained through the incorporation of fibroin fibers in the alginate membrane, even though the fibers were used without any surface treatment to enhance the interfacial adhesion. The incorporation of fibroin fibers improved the tensile strength and also provided a new property to the alginate, that is, the resistance to tear. Moreover, the use of silk fibroin fibers in polymeric composites can result in a material with adequate characteristics for application in the biomaterial field, especially as wound dressings, because of its nontoxic effect to cells, flexibility, and resistance to tear. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3451–3457, 2013     

Preparation and photochromic behavior of borosilicate aluminate glass for smart window and curtain wall applications

Sunlight-induced photochromic glass exhibits attractive application prospects in the field of architecture materials. In this work, a series of borosilicate aluminate photochromic glasses containing AgCl nanocrystals were prepared. The photochromic property and mechanisms were systematically investigated. The color of the glass turned from transparent to black (or dark grey) under the irradiation of 365 nm ultraviolet light (or sunlight). Placing in a dark environment, the color of photochromic glass gradually restores to its initial state. From the results of in situ TEM and XPS measurement, it is found that the photochromic and self-bleaching behavior of borosilicate aluminate glass originated from the formation and decomposition of silver nanoparticles. Utilizing the photochromic and self-bleaching properties of the glass, the transmittance of the glass could be reversibly modulated. The cycle measurement shows excellent repeatability, demonstrating the potential application of AgCl-contained borosilicate aluminate photochromic glass in the fields of smart building windows and curtain walls.     

Recent progress of two-dimensional nanosheet membranes and composite membranes for separation applications

Two-dimensional (2D) materials have emerged as a class of promising materials to prepare high-performance 2D membranes for various separation applications. The precise control of the interlayer nanochannel/sub-nanochannel between nanosheets or the pore size of nanosheets within 2D membranes enables 2D membranes to achieve promising molecular sieving performance. To date, many 2D membranes with high permeability and high selectivity have been reported, exhibiting high separation performance. This review presents the development, progress, and recent breakthrough of different types of 2D membranes, including membranes based on porous and non-porous 2D nanosheets for various separations. Separation mechanism of 2D membranes and their fabrication methods are also reviewed. Last but not the least, challenges and future directions of 2D membranes for wide utilization are discussed in brief.     

Graphene-based membranes for pervaporation processes

Two-dimensional graphene and its derivatives exhibiting distinct physiochemical properties are intriguing building blocks for researchers from a large variety of scientific fields. Assembling graphene-based materials into membrane layers brings great potentials for high-efficiency membrane processes. Particularly, pervaporation by graphene-based membranes has been intensively studied with respect to the membrane design and preparation. This review aims to provide an overview on the graphene-based membranes for pervaporation processes ranged from fabrication to application. Physical or chemical decoration of graphene-based materials is elaborated regarding their effects on the microstructure and performance. The mass transport of pervaporation through graphene-based membranes is introduced, and relevant mechanisms are described. Furthermore, performances of state-of-the-art graphene-based membranes for different pervaporation applications are summarized. Finally, the perspectives of current challenges and future directions are presented.     

Poly(1-trimethylsilyl-1-propyne)/MFI composite membranes for butane separations

The separation of equimolar mixtures of i-butane and n-butane through poly(1-trimethylsilyl-1-propyne)/MFI composite membranes was studied. Membranes were characterized by XRD and SEM. Addition of 50 wt% MFI particles into a PTMSP matrix showed increased permeability and simultaneous improved selectivity in the temperature range 25–200 °C. The best improvement was seen at 150 °C for the composites, giving almost threefold increase in permeability and 56% higher n-butane/i-butane selectivity over the pure polymer. To our knowledge, this is the first successful demonstration of the incorporation of a molecular sieve into a polymer matrix for butane isomer separations. The composite membranes were also tested for separations of n-hexane/2,2-dimethylbutane and p-xylene/o-xylene.     

Composite ceramic membranes from natural aluminosilicates for microfiltration applications

This work concerns to the development and characterisation of support, active layer and tubular composite membranes (CM) from natural aluminosilicates as principal components (clay, bentonite, feldspar, quartz, alumina). The selection of these raw materials was primarily based on their low cost and they are locally produced. In the substrates preparation, the effect of materials compositions, additives, particle sizes, paste rheological properties, and drying-sintering temperatures was investigated. The consolidated ceramic substrates were characterised by SEM, DTA–TG, X-Ray diffraction, Hg intrusion, mechanical resistance, and water flux measurements. Extrusion has been used as the forming process of tubular support. The CM was fabricated depositing a thin active layer by slip-casting method on the support. The CM sintered at 1200 °C showed the best structural characteristics, porosities of 50%, active layer pore size between 0.08 and 0.55 μm. The CM hydraulic permeabilities (10–274 L/h m² kPa) were comparable and greater than several inorganic commercial membranes and CM obtained from other researches. The CM microfiltration effectiveness was tested with different substances from food industry, i.e. slaughterhouse wastewater treatment and goat milk pasteurisation. The obtained results, insoluble residue rejections (100%) and high bacterial removal (87–99%), make the ceramic CM suitable for microfiltration processes.     

Ca-doped zirconia mesoporous coatings for biomedical applications: A physicochemical and biological investigation

In this work, the effects of surface chemistry and nano-topography of un-doped and Ca-doped zirconia coatings were investigated. The study aimed at providing new insight on how to improve the interfacial properties and biocompatibility of metallic and ceramic biomedical implants for hard tissue applications through the surface modification treatments. To this end, pure and Ca-doped zirconia mesoporous coatings were prepared by wet synthesis and structure self-assembly. The physicochemical properties of mesoporous surfaces were investigated by TEM and XRD. In addition, contact angle and XPS unveiled the wettability and surface chemistry of zirconia surfaces. Our findings highlight the role of Ca in increasing stability of the mesoporous structure at high calcination temperature, applied to remove the templating agent. In vitro assays focused on the proliferation of Saos-2 human osteoblastic cells on the meso-structured zirconia coatings, which resulted to be enhanced on Ca-doped surfaces.     

Eggshell derived mesoporous biphasic calcium phosphate for biomedical applications using rapid thermal processing

Biphasic calcium phosphate (BCP) has received much interest for making various bone substitutes since its physicochemical properties can be easily tailored by tuning its phase composition. Due to high temperature processing, it is hard to prepare BCP with nanoscale characteristics. In the present study, we have made an attempt to optimize the heat treatment parameters for the synthesis of BCP with nanoscale characteristics from eggshell derived hydroxyapatite (HA) through rapid thermal processing (RTP). To accomplish this, eggshell derived HA was prepared by wet precipitation method and subjected to RTP at 750°C and 1150°C for 3 and 10 minutes. For comparison we have also studied conventional calcination at 750°C and 1150°C for 3 hours. XRD, FTIR, SEM, EDX, HRTEM, and BET analyses were used to understand the effect of RTP and conventional calcination on eggshell derived HA. Our results indicate that eggshell derived HA on RTP at 1150°C for 3 minutes and 10 minutes can offer nanoscale BCP with good dissolution, bioactivity, cytocompatibility, and mesoporous nature. Hence, RTP can be a potential method to prepare BCP with nanoscale features for biomedical applications.     

Electrosynthesis of pyrrole 3-carboxylic acid copolymer films and nanotubes with tunable degree of functionalization for biomedical applications

Tailoring polypyrrole (PPy), an electroactive polymer, with functional groups to which a variety of bioactive molecules can be tethered is highly attractive for building biological structures on conducting surfaces for a range of biomedical applications. In this respect, we investigate the effects of three independent electrosynthesis parameters, namely the applied potential, the composition of the comonomer solution and the film thickness on the incorporation of carboxylic acid-functionalized pyrrole units (Py-COOH) into polypyrrole/Py-COOH copolymer films. FT-IR, XPS and fluorescence microscopy results show that a larger Py-COOH content is inserted in films electrosynthesized at low potential, that the surface functionality of the copolymer films increases with the molar percentage of Py-COOH in the comonomer solution, and that Py-COOH units are preferentially incorporated in the earlier stage of the electrosynthesis process. The method is further adapted for preparing functionalized PPy copolymer nanotubes with potential application in drug delivery. Specifically, functionalized copolymer nanotubes are electrosynthesized through the template method in polycarbonate membrane. Carboxylic acid groups available at the outer surface of these nanostructures are then derivatized to covalently immobilize poly(ethylene glycol) chains, a protein-repellent polymer, so as to enhance the antifouling properties of these promising delivery vehicles.