Thermal Behavior of Nafion Membranes

The thermal behavior of Nafion-117 membranes was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). TG measurements revealed that the mechanism of thermal degradation of a Nafion membrane in the acid form is different from that of Nafion in the sodium form. The DSC curves for the first heating, for both acid and salt forms, display two endothermic peaks, near 120 and 230°C. The high-temperature peak was assigned to the crystalline domains melting in Nafion, and the low-temperature peak was attributed to a transition into ionic clusters, since this transition exhibits significant changes depending on the nature of the counterion and the degree of hydration.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal characterization of bacterial cellulose–phosphate composite membranes

Cellulose–phosphate composite membranes have been prepared from bacterial cellulose membranes (BC) and sodium polyphosphate solution. The structure and thermal behavior of the new composites were evaluated by X-ray diffraction (XRD), ³¹P-nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG) and thermomechanical analysis (TMA). From XRD analyses the Iα and Iβ cellulose crystalline phases were identified together with crystalline sodium phosphate that covers the cellulose microfibrils as revealed by SEM. ³¹P NMR spectra show peaks assigned to Q⁰ and Q¹ phosphate structures to be compared to the Q² units that characterize the precursor polyphosphate. Glass transition temperature, T _g, obtained from TMA curves and thermal stability obtained from TG and DSC measurements, were observed to be dependent on the phosphate content.     

Thermal stability and decomposition of nafion® membranes with different cations

The thermal decomposition of Nafion has been studied by means of high-resolution and constant heating rate thermogravimetry (TG), under nitrogen and synthetic air atmospheres. Nafion membranes have been studied in acid and salt (alkali chlorides) forms. The TG curves of Nafion with alkali countercations show similar profiles, whichever the atmosphere employed. The kinetics of thermal decomposition of the Nafion-Cs⁺ has also been studied. The method employed to calculate the kinetic parameters and to estimate the polymer lifetime from the data was based on Kissinger's method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, ¹H NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times.     

Thermal behavior of Ca2+ and Cu2+ oxalates obtained by precipitation in homogeneous solution from dimethyl oxalate hydrolysis

Mixed calcium and copper oxalates, with different proportions of Ca²⁺ and Cu²⁺ ions, were precipitated by dimethyl oxalate hydrolysis in homogeneous solution. The compounds were evaluated by means of scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetry (TG), and differential thermal analysis (DTA). The results suggested quantitative precipitation without solid solution formation. From the TG and DTA curves, it was possible to evaluate the Ca²⁺ ion proportion in the solid phase and to confirm the precipitation of the individual species.     

The effect of ferric ions on the conductivity of various types of polymer cation exchange membranes

Recently, rejuvenated interest to fuel cells has posed a number of problems regarding the polymer electrolyte membrane properties and their behaviour in different electrolyte solutions. This work was dedicated to study the conductivity of H⁺-, Fe³⁺- and mixed H⁺/Fe³⁺-forms of cation exchange membranes Neosepta CMS, Nafion 112, 115 and 117 and Selemion HSF under conditions similar to these in the Fe³⁺/Fe²⁺–H₂/H⁺ fuel cell in the range of current densities 0–90 mA/cm². It was found that the conductivities of these membranes in 1.09 M H₂SO₄ solution decrease in the following order: Selemion HSF › Nafion 117 ≈ Nafion 115 ≈ Neosepta CMS › Nafion 112. Conductivities of perfluorinated membranes were discussed in terms of Hsu and Gierke percolation theory [20]. The Fe³⁺-forms of Nafion membranes studied displayed a monotonous decline in the resistance when current increased, which is a manifestation of gradual conversion of the Fe³⁺-form into H⁺-form of these membranes. Unlike the Nafion membranes, the Fe³⁺-forms of Neosepta CMS and Selemion HSF membranes exhibited a sharp jump of resistance at relatively high current densities (more than 70 mA/cm²) that is most probably a result of concentration polarization.     

Transport properties of composite membranes containing silicon dioxide and Nafion

Silicon dioxide (SiO₂) nanoparticles were incorporated into Nafion 115 membranes using the sol–gel method in order to investigate their effect on water retention/transport, proton concentration, effective proton mobility, and proton conductivity. By adjusting the sol–gel reaction time, Nafion/SiO₂ membranes were fabricated with SiO₂ content ranging from 5.9 to 33.3 wt%. Because the density of the membranes decreased with increasing SiO₂ content and because dimensional changes with swelling in water of the composite membranes were less than that of unmodified Nafion 115 despite having increased water content, the theory that rigid scaffolding is formed inside the membrane is supported. Water content increases with increasing SiO₂ content due to void space formed inside the membrane. This increase in water content dilutes the protons in the membrane leading to lower proton concentration and therefore lower proton conductivity. A decreasing effective proton mobility with increasing SiO₂ content, likely due to an increase in the tortuosity of the proton-conducting pathway, also contributes to the decreasing conductivity. However, as evidenced by the similar water vapour permeance values, the SiO₂ nanoparticles do not increase the effective tortuosity of the water vapour transmission pathways.     

Electrochemiluminescence from tris(2,2′-bipyridyl)ruthenium(II)-graphene-Nafion modified electrode

An electrochemiluminescence (ECL) sensor based on Ru(bpy)₃²⁺-graphene-Nafion composite film was developed. The graphene sheet was produced by chemical conversion of graphite, and was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Raman spectroscopy. The introduction of conductive graphene into Nafion not only greatly facilitates the electron transfer of Ru(bpy)₃²⁺, but also dramatically improves the long-term stability of the sensor by inhibiting the migration of Ru(bpy)₃²⁺ into the electrochemically inactive hydrophobic region of Nafion. The ECL sensor gives a good linear range over 1 × 10⁻⁷ to 1 × 10⁻⁴ M with a detection limit of 50 nM towards the determination of tripropylamine (TPA), comparable to that obtained by Nafion-CNT. The ECL sensor keeps over 80% and 85% activity towards 0.1 mM TPA after being stored in air and in 0.1 M pH 7.5 phosphate buffer solution (PBS) for a month, respectively. The long-term stability of the modified electrode is better than electrodes modified with Nafion, Nafion-silica, Nafion-titania, or sol-gel films containing Ru(bpy)₃²⁺. Furthermore, the ECL sensor was successfully applied to the selective and sensitive determination of oxalate in urine samples.     

Study of the corrosion products formed on carbon steel surface in hydrochloric acid solution

Effect of an antibacterial drug, sulfacetamide, IUPAC name N-[(4-aminophenyl) sulfonyl] acetamide (APSA), on the corrosion products formed on carbon steel surface in 1.0?mol?L^?1 HCl solution has been investigated using mass loss, X-ray photoelectron spectroscopy (XPS), and simultaneous thermal and differential scanning calorimetry/differential thermal analysis (TG/DSC/DTA). Mass loss measurements reveal that the corrosion rate of carbon steel is retarded by APSA and that the inhibition efficiency of this inhibitor increases with increasing the concentration. XPS analysis shows that, at this stage, the main product of corrosion is a non-stoichiometric Fe³⁺ oxyhydroxide, consisting of a mixture of FeO(OH) in anhydrous or hydrated forms, containing Cl^? inclusions and adsorbed APSA molecules. The mechanism of inhibition was discussed in light of the chemical structure of the investigated inhibitor. The corrosion products were analyzed using TG/DSC/DTA technique.     

Thermal behaviour and spectroscopic studies of complexes of some divalent transitional metals with 2-benzoil-pyridil-izonicotinoylhydrazone

New complexes of 2-benzoyl-pyridil-isonicotinoylhydrazone (L) with Cu(II), Co(II), Ni(II) and Mn(II), having formula of type [ML₂] SO₄·xH₂O (M = Cu²⁺, Co²⁺, Ni²⁺, x = 2 and M = Mn²⁺, x = 3), have been synthesised and characterised. All complexes were characterised on the basis of elemental analyses, IR spectroscopy, UV–VIS–NIR, EPR, as well as thermal analysis and determination of molar conductivity and magnetic moments. The thermal behaviour of complexes was studied using thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC). The structure of L hydrazone was established by X-ray study on single crystal. The ligand works as tridentate NNO, being coordinated through the azomethine nitrogen, the pyridine nitrogen and carbonylic oxygen. Heats of decomposition, ΔH, associated with the exothermal effects were also determined.     

Nanostructure Restoration of Thermally Reduced Graphene Oxide Electrode upon Incorporation of Nafion for Detection of Trace Heavy Metals in Aqueous Solution

High performance reduced graphene oxide (RGO)‐Nafion (N) thin film electrodes coated on silicon (Si) substrates (RGO‐N/Si) were successfully developed through thermal reduction of GO‐N without delamination from the substrates. The restoration of the RGO‐N nanostructure upon the addition of Nafion was proven by Raman spectroscopy (RS) and field emission scanning electron microscopy, and the restoration mechanism of the RGO‐N nanostructure was proposed. Through the investigation using x‐ray photoelectron spectroscopy (XPS), the polyfluorocarbon from Nafion possessed a function that could prevent the delamination of the RGO sheets from the substrates during the thermal reduction. The RGO‐N/Si samples were later used for the determination of trace heavy metals, such as divalent lead, cadmium and copper ions (Pb²⁺, Cd²⁺ and Cu²⁺, respectively) using square wave anodic stripping voltammetry in a 0.1 M acetate buffer solution (pH 5). Based on the electroanalytical measurements, the RGO‐N/Si samples exhibited a highly linear behavior in the detection of Cd²⁺, Pb²⁺ and Cu²⁺ over the concentration range of 50 nM to 300 nM with detection limits at nM levels. In addition, the RGO‐N/Si samples presented good recoveries of target metals in tap water samples.     

Preparation,Characterization and Luminescence Study of Chitosan Membrane and Powder Forms with Eu3 + and Tb3 +

Chitosan membranes with trivalent lanthanide ion Eu^{3 +} were prepared at a ratio of 3:1 w/w (chitosan:lanthanide). There was no membrane formation at a ratio of 1:1 w/w (chitosan: Eu^{3 +} or Tb^{3 +}); in this case a white solid powder was obtained. Both chitosan compounds were characterized by elemental analysis (CHN), thermal analysis (TG/DTG), scanning electron microscopy (SEM) and luminescence spectroscopy. CHN analysis was performed only for chitosan compounds in powder form, suggesting that these compounds have the general formula QUILn.6H₂O, where QUI = Chitosan and Ln = Eu^{3 +} or Tb^{3 +}. The results of TG/DTG curves for chitosan membranes with Eu^{3 +} ion indicate that the introduction of this metal into the chitosan structure causes gradual degradation in residual carbons, showing lower weight loss in the Eu^{3 +} membranes compared to pure chitosan membrane. Analysis of luminescence demonstrated that chitosan membranes with Eu^{3 +} ion exhibit emission in the visible region, showing emission bands from chitosan and Eu^{3 +} moieties. For chitosan with Eu^{3 +} and Tb^{3 +} ions compounds, in powder form, the analysis of luminescence suggested that chitosan is not transferring energy to the lanthanide ion; however, the chemical region where the lanthanide ion is found breaks the selection rules and favors the emission of these ions.     

In-situ thermal crosslinked PA66/β-cyclodextrin/PA66 nanofibrous membranes with high mechanical strength for removal of heavy metal ions by flow through adsorption

β-cyclodextrin (β-CD) based materials have been studied widely as adsorbents and filter membranes for removing pollutants in air or water applications. The present study aimed to develop a sandwich structure of eletrospun nanofibrous membrane based on β-cyclodextrin and PA66 to achieve the high mechanical strength and flow-through adsorption of heavy metal ions in water. The surface and cross section morphology of PA66/β-cyclodextrin/PA66 nanofibrous membranes (PA66/β-CD/PA66 NMs) were examined using scanning electron microscopy (SEM). The physicochemical and mechanical properties of PA66/β-CD/PA66 NMs were analyzed by differential scanning calorimetry (DSC), thermogravimetric (TG) analysis and universal testing machine. The diameter of β-CD and PA66 electrospun fibers are 300–400 nm and 20–40 nm respectively. PA66/β-CD/PA66 NMs show a loosely arranged fibers and layer by layer structure. The tensile strength increases remarkably for PA66/β-CD/PA66 NMs, from 1.33 MPa of β-CD NMs to 23.17 MPa and the Young's modulus increases from 34.8 MPa to 253.3 MPa. The mechanical behavior of PA66/β-CD/PA66 NMs is a typical brittle fracture, and its microcosmic fracture diagrams are also involved. TGA/DSC results confirm the thermal crosslinking reaction is effective and complete. On the basis of SEM, DSC, TG and mechanical behavior analysis results, the molecular mechanism of in situ thermal crosslinking reaction is discussed. Fe³⁺、Ni²⁺ were used to confirm the ability to absorb heavy metal ions of PA66/β-CD/PA66 NMs. In conclusion, PA66/β-CD/PA66 NMs could be a promising solution for removal of metal ions by flow-through adsorption.     

Thermal characterization of Flemion® membranes substituted by alkali metal cations

The thermal behavior of perfluorosulfonated membranes of three equivalent mass (EW=910, 1000 and 1100 g eq⁻¹) has been studied for membranes in acid form and in the alkali metal countercations substituted samples. The water contents of the membranes decrease progressively with increasing EW and the countercations charge density. The monovalent cations substitutions increase the membranes thermal stability. DSC curves show a single endothermic peak around 120°C that give low peak temperature for low EW and high peak temperature for large cations size. The membrane mechanical properties changed for different EW and temperatures of membranes. Stress-strain analysis showed that K⁺ substituted membranes at both temperatures present a highest YM compared to the other alkali cation substitutions. The thermal properties of perfluorosulfonated membranes depend on the water contents, cation size, temperature and also on EW value.     

Thermal analysis of sulfurization of polyacrylonitrile with elemental sulfur

Thermal analysis of sulfurization of polyacrylonitrile (PAN) with elemental sulfur was investigated by thermogravimetry and differential thermal analysis of the mixture of polyacrylonitrile and elemental sulfur up to 600°C. Due to the volatilization of sulfur, the different heating rate (10 and 20 K min⁻¹) and different mixture proportion of polyacrylonitrile and elemental sulfur were adopted to run the analysis. The different heating rates make the DSC curves of sulfur different, but make the DSC curves of PAN similar. In the DSC curve of sulfur for the heating rate of 20 K min⁻¹ around 400°C, a small exothermic peak occurs at 400°C in the wide endothermic peak around 380∼420°C, indicative of that there is an exothermic reaction around 400°C. In the DSC curves of the mixture, the peaks around 320°C are exothermic as the content of sulfur is below 3.5:1 and endothermic as the content of sulfur is over 4:1, indicating that one of the reactions between PAN and sulfur takes place around 320°C. In the TG curves of the mixture, the mass losses begin at 220°C, and sharply drop down from 280°C. The curves for the low sulfur content obviously show two steps of mass loss, and curves for the high sulfur content show only one step of mass loss, indicative of more sulfur is benefit for the complete sulfurization of PAN. This study demonstrates that the TG/DSC analysis can give the parameter for the sulfurization, even if the starting mixture contains the volatile sulfur.     

Effect on bending behavior of counter cation species in perfluorinated sulfonate membrane–platinum composite

The perfluorinated sulfonate membrane (Nafion ®117)–platinum composites having H⁺, mono- and bivalent metal ions as counter cations in the membranes were prepared and the bending behaviors of the composites actuated by the step voltage were investigated in deionized water. The bending behaviors of all composites have the same tendency as the composites to bend quickly to the anode side just after applying the step voltage and gradually to bend back to the cathode side in spite of keeping on the application. However, they show differences in the bending rate and the maximum displacement to the anode side just after applying the step voltage, which are influenced by counter cation species in the membrane. In particular, the composite having Li⁺ has the largest maximum displacement (about 1.1 mm) to the anode side. The relationship between the maximum displacements of the composites and water states in the membranes were studied. The maximum displacements of the composites depend on the water content in the membranes. In both series of the composites having mono- and bivalent metal ions, the maximum displacements increase with increasing water content, except the composites having Rb⁺ and Sr²⁺ which belong to fifth period in the periodic table. In spite of the result that the water content in the membrane having H⁺, which is about 20wt%, is nearly equal to that in the membrane having Na^a, the maximum displacement of the composite having H⁺ is only about one-third as large as that of the composite having Na⁺. The water structures in the membranes were investigated by using differential scanning calorimetry (DSC). The DSC endothermograms obtained indicate that the freezing water in the membrane having H⁺ has a much stronger interaction with sulfonate groups and counter cations than that in the membrane having Na⁺. It is concluded that the content and structure of the freezing water in the membrane have a profound effect on the bending behavior of the composite. © 1998 John Wiley & Sons, Ltd.     

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)₃²⁺ immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.     

Glass transition temperature and thermal decomposition of cellulose powder

Cellulose powder and cellulose pellets obtained by pressing the microcrystalline powder were studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermal gravimetry (TG). The TG method enabled the assessment of water content in the investigated samples. The glass phase transition in cellulose was studied using the DSC method, both in heating and cooling runs, in a wide temperature range from −100 to 180 °C. It is shown that the DSC cooling runs are more suitable for the glass phase transition visualisation than the heating runs. The discrepancy between glass phase transition temperature T _g found using DSC and predictions by Kaelbe’s approach are observed for “dry” (7 and 5.3% water content) cellulose. This could be explained by strong interactions between cellulose chains appearing when the water concentration decreases. The T _g measurements vs. moisture content may be used for cellulose crystallinity index determination.     

Thermal analysis of water and magnesium hydroxide content in commercial pharmaceutical suspensions milk of magnesia

A standard protocol was developed to determine the water content by thermal analysis of milk of magnesia (MoM). Differential scanning calorimetry (DSC) and thermogravimetry (TG) were used in a novel manner for examining the physical characteristics of the commercial pharmaceutical suspensions. Moisture analyzer and oven-dry methods validate the proposed protocol. MoM consists primarily of water and magnesium hydroxide [Mg(OH)₂]. Experimental design of the thermal analysis parameters were considered including sample size, flowing atmosphere, sample pan, and heating rate for both DSC and TG. The results established the optimum conditions for minimizing heat and mass transfer effect. Sample sizes used were: (5?C15?mg) for DSC and (30?C50?mg) for TG. DSC analysis used crimped crucibles with a pinhole, which allowed maximum resolution and gave well-defined mass (water) loss. TG analysis used a heating rate of 10?°C/min^?1 in an atmosphere of nitrogen. The heat of crystallization, heat of fusion, and heat of vaporization of unbound water are 334, 334, and 2,257?Jg^?1, respectively (Mitra et al. Proc NATAS Annu Conf Therm Anal Appl 30:203?C208, 2002). The DSC average water content of (MoM) was 80?wt% for name brand and 89.5?wt% for generic brand, based on the relative crystallization, melting and vaporization heats/Jg^?1 of distilled water in the recently purchased (2011) MoM samples. The TG showed a two-step process, losing water at 80?C135?°C for unbound water and bound water (MgO·H₂O) at 376?C404?°C, yielding a total average water loss of 91.9?% for name brand and 90.7?% for generic brand by mass. The difference between the high-temperature TG and the lower-temperature DSC can be attributed for the decomposition of magnesium hydroxide or MgO·H₂O. Therefore in performing this new approach to water analysis by heating to a high temperature decomposed the magnesium hydroxide residue. It was determined that the TG method was the most accurate for determining bound and unbound water.     

Dehydration studies of Co(II), Cu(II) and Zn(II) methanesulfonates

The dehydration process of Co(II), Cu(II) and Zn(II) methanesulfonates was studied by thermogravimetry/derivative thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC) techniques in dynamic N₂ atmosphere. The TG/DTG curves show that all of them contain four crystallization water molecules, which are lost in two steps. The peak temperature and dehydration enthalpies ΔH were measured from DSC curves for each compound. The effect of procedural variables on the TG and DSC curves was investigated. In this work, the procedural variables included heating rate, Al pan state (unsealed and sealed) and sample mass.