Sulphonated Tetramethyl Poly(ether ether ketone)/Epoxy/Sulphonated Phenol Novolac Semi-IPN Membranes for Direct Methanol Fuel Cells

The sulphonated phenol novolac (PNBS) which was used as a curing agent of epoxy was synthesised from phenol novolac (PN) and 1,4-butane sultone and confirmed by FTIR and H-1 NMR. The degree of sulphonation (DS) in PNBS was calculated by H-1 NMR. The semi-IPN membranes composed of sulphonated tetramethyl poly(ether ether ketone) (STMPEEK) (the value of ion exchange capacity is 2.01 meq g(-1)), epoxy (TMBP) and PNBS were successfully prepared. The semi-IPN membranes showed high thermal properties which were measured by differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) With the introduction of the corss-linked TMBP/PNBS, the mechanical properties, dimensional stability, methanol resistance and oxidative stability of the membranes were improve in comparison to the pristine STMPEEK membrane.

Implantation of Nafion (R) ionomer into polyvinyl alcohol/chitosan composites to form novel proton-conducting membranes for direct methanol fuel cells

A series of cost-effective, proton-conducting composite membranes, comprising of Nafion (R) ionomer, chitosan (CS). and polyvinyl alcohol (PVA), is successfully prepared. By taking advantage of the strong electrostatic interactions between Nafion (R) ionomer and CS component, Nafion ionomer is effectively implanted into the PVA/CS composite membranes, and improves proton conductivity of the PVA/CS composite membranes. Furthermore, this effect dramatically depends on the composition ratio of PVA/CS, and the optimum conductivity is obtained at the PVA/CS ratio of 1:1. The developed composite membranes exhibit much lower methanol permeability compared with the widely used Nafion (R) membrane, indicating that these novel membranes have great potential for direct methanol fuel cells (DMFCs).

Highly conductive, methanol resistant fuel cell membranes fabricated by layer-by-layer self-assembly of inorganic heteropolyacid

Layer-by-layer (LBL) self-assembly is a simple and elegant method of constructing organic-inorganic composite thin films from environmentally benign aqueous solutions. In this paper, we utilize this method to develop proton-exchange membranes for fuel cells. The multilayer film is constructed onto the surface of sulfonated poly(arylene ether ketone) (SPAEK-COOH) membrane by LBL self-assembly of polycation chitosan (CTS) and negatively charged inorganic particle phosphotungstic acid (VIA). The highly conductive inorganic nanoparticles ensure SPAEK-COOH-(CTS/PTA)(n) membranes to maintain high proton conductivity values up to 0.086 S cm(-1) at 25 degrees C and 0.24S cm(-1) at 80 degrees C, which are superior than previous LBL assembled electrolyte systems.

Novel sulfonated poly(arylene ether ketone) copolymers bearing carboxylic or benzimidazole pendant groups for proton exchange membranes

A novel strategy in which the benzimidazole group and sulfonic group are simultaneously attached to an aromatic polymer has been reported in this paper. For this purpose, sulfonated poly(arylene ether ketone) copolymers containing carboxylic acid groups (SPAEK-x-COOH, x refers to the molar percentage Of sulfonated repeating units) are prepared by the aromatic nucleophilic polycondensation of sodium 5,5'-carbonyl-bis(2-fluobenzene-sulfonate) (SDFBP), 4,4'-difluorobenzophenone (DFBP) and phenolphthalin (PPL). Then the carboxylic acid groups attached to the SPAEK-x-COOH are transformed to benzimidazole units through condensation reactions (referred to as SPAEK-x-BI). Fourier transform infrared spectroscopy and H-1 NMR measurements are used to characterize and confirm the structures of these copolymers.

Polyelectrolyte complexes of chitosan and phosphotungstic acid as proton-conducting membranes for direct methanol fuel cells

Polyelectrolyte complexes (PECs) of chitosan and phosphotungstic acid have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Phosphotungstic acid can be fixed within PECs membranes through strong electrostatic interactions, which avoids the decrease of conductivity caused by the dissolving of phosphotungstic acid as previously reported. Scanning electron microscopy (SEM) shows that the PECs membranes are homogeneous and dense. Fourier transform infrared spectroscopy (FTIR) demonstrates that hydrogen bonding is formed between chitosan and phosphotungstic acid. Thermogravimetric analysis (TGA) shows that the PECs membranes have good thermal stability up to 210 degrees C. The PECs membranes exhibit good swelling properties and low methanol permeability (P, 3.3 x 10(-7) cm(2) s(-1)). Proton conductivity (sigma) of the PECs membranes increases at elevated temperature, reaching the value of 0.024 S cm(-1) at 80 degrees C.

Effective interface of a composite membrane serving as an ideally ultrathin barrier layer

A novel idea relating to the selective barrier layer of a composite membrane is described. The effective interface of the composite membrane could act as a barrier layer which could be controlled to an ideally ultrathin thickness. A new type of polyamide composite membrane was prepared according to this idea, which possessed permeability and chemical resistance more than one magnitude greater than those of ordinary polyamide composite membranes. Copyright (C) 1996 Elsevier Science Ltd.

Truly chlorine-resistant polyamide reverse osmosis composite membrane

Truly chlorine-resistant polyamide reverse osmosis composite membranes were prepared by cross-linking the interface of the composite membrane. Such membranes possessed chlorine resistance one order of magnitude more than those of the commercially used polyamide composite membranes. The effect of the degree of cross-linking on chlorine resistance was also described. (C) 1996 John Wiley & Sons, Inc.

Application of mesoporous silica for the oral delivery of poorly water-soluble drugs

The objective of this thesis was to improve the dissolution rate of the poorly waters-soluble drug, fenofibrate by processing it with a high surface area carrier, mesoporous silica. The subsequent properties of the drug – silica composite were studied in terms of drug distribution within the silica matrix, solid state and release properties. Prior to commencing any experimental work, the properties of unprocessed mesoporous silica and fenofibrate were characterised (chapter 3), this allowed for comparison with the processed samples studied in later chapters. Fenofibrate was a highly stable, crystalline drug that did not adsorb moisture, even under long term accelerated storage conditions. It maintained its crystallinity even after SC-CO2 processing. Its dissolution rate was limited and dependent on the characteristics of the particular in vitro media studied. Mesoporous silica had a large surface area and mesopore volume and readily picked up moisture when stored under long term accelerated storage conditions (75% RH, 40 oC). It maintained its mesopore character after SC-CO2 processing. A variety of methods were employed to process fenofibrate with mesoporous silica including physical mixing, melt method, solvent impregnation and novel methods such as liquid and supercritical carbon dioxide (SC-CO2) (chapter 4). It was found that it was important to break down the fenofibrate particulate structure to a molecular state to enable drug molecules enter into the silica mesopores. While all processing methods led to some increase in fenofibrate release properties; the impregnation, liquid and SC-CO2 methods produced the most rapid release rates. SC-CO2 processing was further studied with a view to optimising the processing parameters to achieve the highest drug-loading efficiency possible (chapter 5). In this thesis, it was that SC-CO2 processing pressure had a bearing on drug-loading efficiency. Neither pressure, duration or depressurisation rate affected drug solid state or release properties. The amount of drug that could be loaded onto to the mesoporous silica successfully was also investigated at different ratios of drug mass to silica surface area under constant SC-CO2 conditions; as the drug – silica ratio increased, the drug-loading efficiency decreased, while there was no effect on drug solid state or release properties. The influence of the number of drug-loading steps was investigated (chapter 6) with a view to increasing the drug-loading efficiency. This multiple step approach did not yield an increase in drug-loading efficiency compared to the single step approach. It was also an objective in this chapter to understand how much drug could be loaded into silica mesopores; a method based on the known volume of the mesopores and true density of drug was investigated. However, this approach led to serious repercussions in terms of the subsequent solid state nature of the drug and its release performance; there was significant drug crystallinity and reduced release extent. The impact of in vitro release media on fenofibrate release was also studied (chapter 6). Here it was seen that media containing HCl led to reduced drug release over time compared to equivalent media not containing HCl. The key findings of this thesis are discussed in chapter 7 and included: 1. Drug – silica processing method strongly influenced drug distribution within the silica matrix, drug solid state and release. 2. The silica surface area and mesopore volume also influenced how much drug could be loaded. It was shown that SC-CO2 processing variables such as processing pressure (13.79 – 41.37 MPa), duration time (4 – 24 h) and depressurisation rate (rapid or controlled) did not influence the drug distribution within the SBA- 15 matrix, drug solid state form or release. Possible avenues of research to be considered going forward include the development and application of high resolution imaging techniques to visualise drug molecules within the silica mesopores. Also, the issues surrounding SBA-15 usage in a pharmaceutical manufacturing environment should be addressed.

Studies on the curing of short polyester fiber-polyurethane elastomer composite with different interfacial bonding agents

The cure characteristics of short fiber-polyurethane elastomer were studied with respect to different fiber-matrix bonding agents. A hexamethylenetetramine- resorcinol -hydrated silica based bonding agent was found to affect the stability of the composite. A new bonding agent, TP resin, based on polymeric toluenediisocyanate and polypropylene glycol has been developed. Cure characteristics of the composite with and without TP resin at different fiber loadings were also compared. Minimum torque, scorch time and optimum cure time increased with fiber content. Maximum torque was consistently higher with TP resin at all fiber loadings.

Composites PVDF-TrFE/BT used as bioactive membranes for enhancing bone regeneration

In this paper a piezoelectric composite membranes were developed for charge generator to promoter bone regeneration on defects sites. Is known that the osteogenesis process is induced by interactions between biological mechanisms and electrical phenomena. The membranes were prepared by mixing Barium Titanate (BT) powders and PVDF-TrFE (PVDF:TrFE = 60:40 mol%) on dimethylformamide medium. This precursor solution was dried and crystallized at 100degreesC for 12 hours. Composites membranes were obtained by following methods: solvent casting (SC), spincoating (SP), solvent extraction by water addition (WS) and hot pressing (HP).The microstructural analysis performed by SEM showed connectivity type 3-0 and 3-1 with high homogeneity for samples of ceramic volume fraction major than 0.50. Powder agglomerates within the polymer matrix was evidenced were observed for composites with the BT volume fraction major than 40%. The composite of ceramic fraction of 0.55 presented the best values of remanent polarization (similar to33 muC/cm(2)), but the flexibility of these composites with the larger ceramic fraction was significantly affected.For in vivo evaluation PVDF-TrFE/BT 90/10 membranes with 3cm larger were longitudinally implanted under tibiae of male rabbit. After 21 days the animals were sacrificed. By histological analyses were observed neo formed bone with a high mitotic activity. In the interface bone-membrane was evidenced a pronounced callus formation. These results encourage further applications of these membranes in bone-repair process.

Luminescent multifunctional biocellulose membranes

Luminescent biocellulose membranes were obtained by incorporation of ethanolic solutions of the europium compounds [Eu(BTFAC)3(H2O)2], [Eu(BTFA) 3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] (BTFAC- 4,4,4-Trifluoro-1- phenyl-1,3-butanedione DBSO- dibenzyl sulfoxide, PTSO- p-Tolyl sulfoxide and FSO- phenyl sulfoxide). Selfsustainable semi-transparent composite membranes were obtained showing strong emission under UV exctiation. The antenna hole played by the ligands was observed to be more efficient in the composite membranes than in the precursor complexes which by themselves are also strong red emitter compounds. These new multifuctional membranes could find application in different areas as phosphors and UV→Visible energy converting devices. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).

Nanocompósitos baseados em celulose bacteriana para aplicações ópticas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Poly(2,5-bibenzimidazole) Membranes: Physico-Chemical Characterization Focused on Fuel Cell Applications

Membranes of Poly(2,5-benzimidazole) (ABPBI), prepared by polycondensation in polyphosphoric acid, were characterized from the fuel cell application point of view: mechanical properties of the membranes for different acid doping levels, thermal stability, permeability for the different gases/vapors susceptible of use in the cell (hydrogen, oxygen, methanol and ethanol), electro-osmotic water drag coefficient, oxidation stability to hydroxyl radicals, phosphoric acid leaching rate and, finally, in-plane membrane conductivity. ABPBI membranes presented an excellent thermal stability, above 500 degrees C in oxygen, suitable mechanical properties for high phosphoric acid doping levels, a low methanol and ethanol limiting permeation currents, and oxygen permeability compared to Nafion membranes, and a low phosphoric acid leaching rate when exposed to water vapor. On the contrary, hydrogen permeation current was higher than that of Nafion, and the chemical stability was very limited. Membrane conductivity achieved 0.07 S cm(-1) after equilibration with a humid environment. Fuel cell tests showed reasonable good performances, with a maximum power peak of 170 mW cm(-2) for H-2/air at 170 degrees C operating under a humidified hydrogen stream, 39.9 mW cm(-2) for CH3OH/O-2 at 200 degrees C for a methanol/water weight ratio of 1: 2, and 31.5 mW cm(-2) for CH3CH2OH/O-2 at the same conditions than for methanol. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.014207jes] All rights reserved.

Enzymatic Solid-Phase Reactor Based on Silica Organofunctionalized with p-Phenylenediamine for Electrochemical Detection of Phenolic Compounds

A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.