Preparation of zeolite-incorporated PDMS membranes for pervaporation separation of isopropanol-water mixtures

ZSM-5 zeolite-incorporated poly(dimethyl siloxane) membranes were prepared and molecular dispersion of zeolite in the membrane matrix was confirmed by scanning electron microscopy. After studying the behavior of membrane swelling at 30°C, the membranes were subjected to pervaporation separation of isopropanol-water mixtures at 30, 40 and 50°C. The effects of zeolite loading and feed composition on the pervaporation performances of the membranes were analyzed. Both permeation flux and selectivity increased simultaneously with increasing zeolite content in the membrane matrix. This was discussed on the basis of the enhancement of hydrophobicity, selective adsorption, and the establishment of molecular sieving action. The membrane containing the highest zeolite loading (30 mass%) exhibits the highest separation selectivity of 80.84 and flux of 6.78 × 10^?2kg/m²h at 30°C for 5 mass% of isopropanol in the feed. From the temperature dependency of diffusion and permeation values, the Arrhenius activation parameters were estimated. A pure membrane (M) exhibits higher E_p and E_D values compared to zeolite-incorporated membranes, signifying that permeation and diffusion require more energy for transport through a pure membrane, owing to its dense nature. Obviously, zeolite-incorporated membranes require less energy due to their molecular sieving action attributed to the presence of straight and sinusoidal channels in the framework of zeolite. All the zeolite-incorporated membranes exhibit positive ΔH_s values, suggesting that the heat of sorption is dominated by the Henry's mode of sorption.     

Investigation on Three-Dimensional Solubility Parameters for Explanation and Prediction of Swelling Degree of Polydimethylsiloxane Pervaporation Membranes

Using polydimethylsiloxane (PDMS) as a basic matrix to prepare ethanol and butanol permselective pervaporation membranes is a vibrant field. Many studies have verified that the three-dimensional Hansen solubility parameters (HSP) theory offers a valid explanation for the swelling performance of ethanol and butanol in PDMS. Five parameters (δ_D, δ_P, δ_H, δ_t, and R_a) are defined in HSP theory which can be individually used to explain the interaction strength between a solvent and a polymer. However, for the above five parameters, which one is the most effective parameter for deciding the swelling degree still needs to be determined. In this study, a commonly used hydroxy-terminated PDMS precursor was adopted to prepare the PDMS network. The HSP of the chosen PDMS precursor was measured by an advanced “solubility-rating” method. The special software package HSPiP (4.1.03), purchased from the HSPiP team, was used to process the “solubility-rating” results. The equilibrium swelling degree (Q value) of the PDMS network in water, ethanol, butanol, and toluene was measured and the relationships between the five HSP parameters of the solvents and the logarithmic equilibrium swelling degree, log(Q), were discussed. It was found that the measured polar parameter, δ_P, of PDMS was 0.12 MPa^0.5. The measured hydrogen bonding parameter, δ_H, was larger than δ_P, attaining a value of 8.6 MPa^0.5, because the hydroxy groups directly contributed to the hydrogen bonding solubility parameter, δ_H. With respect to the relationships between log(Q) and δ_D, δ_P, δ_H, δ_t, and R_a, linear relationships existed after plotting log(Q) vs. δ_P and log(Q) vs. δ_H. The linear relation degree of the fitted lines was 0.995 and 0.989, respectively. Their standard deviations were 0.149 and 0.232, respectively. Therefore, a better linear relationship existed between log(Q) and δ_P than the other solubility parameters. This indicated that the polar interaction was the main effect for deciding the swelling degree of the PDMS network in water and alcohol systems.     

Modeling Sorption Behavior for Ethanol/Water Mixtures in a Cross-linked Polydimethylsiloxane Membrane Using the Flory-Huggins Equation

The sorption behaviors of aqueous ethanol solutions in a polydimethylsiloxane (PDMS) membrane at 25°C were investigated in this study. The sorption isotherms for the ethanol and water binary mixtures were experimentally determined. The water uptake reached a maximum at a concentration of 80 wt% ethanol, and the partial water uptakes were even higher than the pure water solubility for 10–95 wt% ethanol solutions in the PDMS membrane, which implies the presence of a strong synergistic effect due to the ethanol copermeant. The Flory-Huggins equation was utilized to predict the sorption levels at various ethanol/water compositions. The binary Flory-Huggins interaction parameters obtained from pure solvent sorption experiments (χ_iM ) and the ethanol/water vapor liquid equilibrium data (χ ₁₂) were used in the construction of the model for predicting the partial penetrant solubilities. Using constant χ_ij parameters could not render satisfactory predictions; therefore, concentration-dependent expressions for either χ ₁₂ or χ_iM were employed to improve the prediction power. We found that constant or concentration dependent χ ₁₂ parameters had little impact on the predicted sorption, whereas the modified concentration-dependent χ_iM values greatly improved the modeling precision.     

Photoelectron spectroscopy of some thiocyanates,isocyanates and isothiocyanates

Photoelectron spectra of some thiocyanates (RSCN, R = CH₃, C₂H₅, n-C₄H₉), isocyanates (RNCO, R = C₂H₅, n-C₄H₉) and isothiocyanates (RNCS, R = C₂H₅, n-C₄H₉) have been measured, to study interactions between nonbonding and π orbitals, mainly localized on the SCN, NCO or NCS fragments. The spectral interpretation of CH₃SCN is based on semiempirical CNDO/S calculations, sum-rule considerations, and intensity differences between He(I) and HE(II) spectra. For the larger molecules, comparison of the spectra is used as an aid in the interpretation. In a number of aromatic isocyanates (o?, m?, p-tolylisocyanate and m?, p-chlorophenylisocyanate), interactions between the isocyanate group and the highest occupied π and σ orbitals of the phenyl ring are studied. Spectra are assigned on the basis of semiempirical INDO/S calculations.     

Synthesis and properties of side-chain-type ion exchange membrane PEEK-g-StSO3Na for bipolar membranes

Side-chain-type ion exchange membranes (PEEK-g-StSO₃Na) were prepared by grafting poly (ether ether ketone) (PEEK) containing propenyl groups with sodium sulfonic styrene (StSO₃Na) and KH570. PEEK was synthesized by the aromatic nucleophilic polycondensation reaction of 4,4′-difluorobenzophenone, bisphenol A and diallylbisphenol A. The synthesized copolymers with the -SO₃Na group on the side chain of polymers possessed high molecular weights. The cross-linking reaction was carried out through a sol-gel reaction of the trimethoxysilane group. The copolymer membranes exhibited excellent mechanical properties due to their aromatic structure extending through the backbone and flexible StSO₃Na aliphatic chains. The ion exchange capacities (IECs) of the membranes ranged from 2.27 to 2.50 mmol g⁻¹ and the water content ranged from 107.2 to 126.1%, with both parameters increasing with StSO₃Na grafting degree. The H⁺ permeability of copolymer membranes increased with increasing IEC, reaching value above 0.3056 mol/L at 2 h, which is higher than that of Nafion^® 117 at the same measurement condition. They displayed reasonably high H⁺ permeability due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water occupation, and the lower AC impedance of the bipolar membrane.     

Studies on the Formation of β-Cyclodextrin/Alkylcobaloxime Inclusion Complexes by Using NMR Methods

Abstract

It has been established that alkylcobaloxime(R=i-C₄H₉, n-C₄H₉, n-C_sH₁₁, c-C₆H₁₁, PhCH₂) and β-cyclodextrin form a kind of 1: 1 inclusion complexes in aqueous solution by ¹H NMR spectroscopy. Ka and ?ΔG^θ were calculated according to chemical shift changes of different probe protons. The stability constant(Ka) has been found increasing in the order: PhCH₂ > n-C₅H₁₁ > c-C₆H₁₁ > i-C₄H₉ > n-C₄H₉.     

Polyelectrolyte Nanocomposite Membranes Using Surface Modified Nanosilica for Fuel Cell Applications

The preparation and characterization of a new type of nanocomposite polyelectrolyte membrane (PEM), based on Nafion® (E. I. du Pont de Nemours and Co., Ltd., for its copolymer of tetrafluoroethylene and perfluorinated vinyl ether) and sulfonic acid (-SO₃H) or phosphotungstic acid (PWA) modified nanosilica (Si-SO₃H or Si-PWA, respectively), for direct methanol fuel cell (DMFC) applications are described. Physical characteristics of these manufactured nanocomposite membranes were investigated by scanning electron microscopy (SEM), water uptake, methanol permeability and ion exchange capacity, as well as proton conductivity. The Nafion®/Si-PWA and Nafion®/Si-SO₃H membranes showed higher proton conductivity, lower methanol permeability and, as a consequence, a higher selectivity parameter, in comparison to the neat Nafion® or Nafion®/pristine nanosilica membranes. The obtained results indicated that both the Nafion®/Si-PWA and Nafion®/Si-SO₃H membranes could be utilized as promising polyelectrolyte membranes for direct methanol fuel cell applications.     

Sorption of Organic Solvents in Poly(Dimethyl Siloxane) Membrane. II. Effect of Sorption on the Polymer Crystals upon Cooling

Polymer crystalline properties in poly(dimethyl siloxane) (PDMS) film after solvation by various solvents was determined using low temperature differential scanning calorimetry (DSC). At various solvent uptake levels, the crystalline thermal properties of the solvated polymer were modified to different extents as revealed by the shifts in crystalline melting point (T_m) and its enthalpy (ΔH_m). Water uptake in PDMS was very limited (<0.01 g/g) and T_m did not significantly change during the sorption process. For toluene and cyclohexane penetrants, T_m moved toward a much lower temperature depending on the sorption levels. At low solvent uptakes, the T_m values decreased linearly with solvent uptakes due to formation of a miscible phase. Beyond a threshold, the T_m remained stable and an additional penetrant fusion peak appeared, implying the onset of a microphase separation phenomenon. The ΔH_m values for the swollen membranes were decreased, with the exception of the water penetrant. This indicates that a lower percentage of polymer chains were involved in the crystalline domain for swollen PDMS.     

Mössbauer spectroscopic characterisation of catalysts obtained by interaction between tetra-n-butyl-tin and silica or silica supported rhodium

Mössbauer spectroscopy at 78 K was used to study the interaction between tetra-n-butyl-tin and the surfaces of silica or silica supported rhodium. At room temperature, the tetra-n-butyl-tin was physically adsorbed on the surfaces. After reaction under hydrogen at 373 K, the formation of grafted organometallic fragments on the Rh surface was confirmed whereas with pure silica, ≡SiO-Sn(n-C₄H₉)₃ moieties were observed. After treatment at 523 K, the rhodium grafted organometallic species was completely decomposed and there was formation of a defined bimetallic RhSn compound.     

Organosilane modified silica/polydimethylsiloxane mixed matrix membranes for enhanced propylene/nitrogen separation

Gas transport behaviors of oxygen (O₂), nitrogen (N₂) and propylene (C₃H₆) in polydimethylsiloxane (PDMS) mixed matrix membranes (MMM) containing modified silica (SiO₂) nanoparticles are presented. Two surface modified SiO₂ nanoparticles, silica dimethyloctyl silane (Si-DMOS) and silica dimethylphenyl silane (Si-DMPS), were used as fillers. Surface modification was carried out through silanization, which was confirmed via Fourier transform infrared spectroscopy. From elemental analysis, degrees of modifications on Si-DMOS and Si-DMPS were estimated to be 29.64% and 79.89%, respectively. Field emission scanning electron microscopy showed uniform distribution of the modified SiO₂ fillers in MMMs. Both MMMs exhibited reduced O₂ and N₂ permeabilities as compared to pure PDMS, while enhanced C₃H₆ permeabilities were observed. Consequently, C₃H₆/N₂ permselectivities were increased by 35 and 44% in MMMs filled with Si-DMOS and Si-DMPS, respectively. Results revealed that permeability was dependent on penetrant diffusivities, a parameter related to the structure of MMMs. Density measurements and differential scanning calorimetry were performed to elucidate the changes in MMM properties which affected the permeation behaviors of O₂, N₂ and C₃H₆. Overall, both Si-DMOS and Si-DMPS show potential as fillers for the enhancement of PDMS permeation performance.     

Preparation of poly(vinyl alcohol)–silicone based hybrid membranes for the pervaporation separation of water–acetic acid mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis followed by condensation. The obtained membranes were characterized by Fourier transform infrared spectroscopy, wide-angle x-ray diffraction and differential scanning calorimetry. A remarkable decrease in degree of swelling was observed with increasing TEOS content in membranes and is attributed to the formation of hydrogen bonding and covalent bonds in the membrane matrix. The pervaporation performance of these membranes for the separation of water–acetic acid mixtures was investigated in terms of feed concentration and the content of TEOS used as cross-linking agent. The membrane containing 1 : 2 mass ratio of PVA and TEOS gave the highest separation selectivity of 1116 with a flux of 3.33 × 10^?2kg/m²h at 30°C for 10 mass% of water in the feed. Except for membrane M-1, the observed values of water flux are close to the values of total flux in the investigated composition range, signifying that the developed membranes are highly water selective. From the temperature dependence of diffusion and permeation values, the Arrhenius apparent activation parameters have been estimated. The resulting activation energy values obtained, showing that water permeation is lower than that of acetic acid, suggest that the membranes have higher separation efficiency. The activation energy values calculated for total permeation and water permeation are close to each other for all the membranes except membrane M-1, signifying that coupled-transport is minimal because of the higher selective nature of membranes. The negative heat of sorption values (ΔH _s) for water in all the membranes suggests a Langmuir mode of sorption.     

Pressure broadening and collisional shift of the Rb D2 absorption line by CH4, C2H6, C3H8, n-C4H10, and He

The pressure broadening and shift rates of the rubidium D2 absorption line 5²S_1/2→5²P_3/2 (780.24 nm) with CH₄, C₂H₆, C₃H₈, n-C₄H₁₀, and He were measured for pressures ≤80 Torr using high-resolution laser spectroscopy. The broadening rates γ_B for CH₄, C₂H₆, C₃H₈, n-C₄H₁₀, and He are 28.0, 28.1, 30.5, 31.3, and 20.3 (MHz/Torr), respectively. The corresponding shift rates γ_S are −8.4, −8.8, −9.7, −10.0, and 0.39 (MHz/Torr), respectively. The measured rates of Rb for the hydrocarbon buffer gas series of this study are also compared to the theoretically calculated rates of a purely attractive van der Waals difference potential. Good agreement is found to exist between measured and theoretical rates.     

One-step fabrication of surface-relief diffusers by stress-induced undulations on elastomer

In this study, we demonstrated that microscale surface undulations induced by acid treatment could serve as the surface relief on diffusers coated with a layer of PDMS polymer. Since the orientation of undulations was found to be always disordered, these undulations would scatter light uniformly. The periodicity of the undulations could be adjusted by the control of duration of the dipping of the elastomer into H₂SO₄/HNO₃ solutions and by the volume ratio of H₂SO₄/HNO₃ the solution, resulting in the modulation of diffusing ability of diffusers. The optical properties, transmittance, and light diffusivity, were characterised. This proposed approach offers potential for mass production of surface-relief diffusers. In addition, the proposed method allows the creation of undulations on arbitrary substrates.     

Novel volumetric analysis technique for characterizing the solubility and diffusivity of hydrogen in rubbers

We introduce a volumetric analysis technique to characterize the solubility of hydrogen dissolved in polymers and its diffusion coefficient by electrical capacitance measurement electrodes to determine the water level in graduated cylinders. This new and simple technique measures the volume of hydrogen released from rubber inside a graduated cylinder after a sample is exposed to high-pressure hydrogen and subsequent decompression. A diffusion analysis program is utilized to determine the total uptake (C₀) and diffusivity (D) of hydrogen, which are used to calculate the solubility (S) and permeability (P). This method is applied to spherical rubber samples of nitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluoroelastomer (FKM), which are potential sealing materials for H₂ energy infrastructures. C₀ follows Henry's law for all samples. No sample size and pressure dependence is observed for S, whereas an appreciable size dependence for the three rubbers is detected for D. The uncertainty is evaluated by considering uncertainty factors that affect the measurement. The correlation between D and density of rubber is found. The developed method can be utilized as a standard test for the transport properties versus pressure of various polymer membranes regardless of the sample shapes and size.     

Spin-glass behavior and magnetic splitting in molecular magnetic materials {[N(n-C4H9)4][MIIFeIII(C2O4)3]}n (M = Co, Mn)

The mixed valence character and the antiferromagnetic coupling in the molecular magnetic materials {[N(n-C₄H₉)₄][M^IIFe^III(C₂O₄)₃]}_n (M = Co, Mn) were investigated by Mössbauer spectroscopy and magnetic measurements. In the material {[N(n-C₄H₉)₄][CoFe(C₂O₄)₃]}_n, the appearence of the spin-glass phase transition temperature and the magnetic phase transition under zero-field-cooled AC magnetic measurements were studied in the temperature range 5–100 K. In the Mössbauer spectra of {[N(n-C₄H₉)₄][MnFe(C₂O₄)₃]} a magnetic splitting was observed below 30 K. The appearance of the magnetic splitting indicates the occurrence of magnetic ordering in this complex. The hyperfine parameters show that the electronic state of iron is high-spin Fe³⁺.     

Mössbauer spectroscopic studies of (n-C n H2n +1NH3)2SnX6 (n=0-4; X = Cl or Br) and their related complexes

Complexes of the type (n-C _n H_2n +1NH₃)₂SnX₆ (0n 4 and X=Cl or Br) have been investigated with a variety of physico-chemical techniques. The structural phase transitions were found in some of these complexes. The temperature dependence of the Mössbauer spectral absorption area for (C₂H₅NH₃)₂SnCl₆ and (C₂H₅NH₃)₂SnBr₆ changed sharply at phase transition temperatures. The temperature dependences for (n-C₄H₉NH₃)₂SnCl₆ and (n-C₄H₉NH₃)₂SnBr₆ decreased gradually with an increase in temperature. The correlation between the temperature dependence of the spectral absorption area and the motion of n-C _n H_2n+1NH₃ ⁺ ions is discussed.     

Atomistic simulation of gas phase atoms with RADII through polysiloxane

Abstract

Molecular dynamics simulations have been carried out to examine mechanisms of small molecules' diffusion in amorphous polymer membranes. Polydimethylsiloxane (PDMS) structure consisting of three chains of 50 monomers each, were folded into periodic cells, generated by rotational isomeric state (RIS) method at a prescribed temperature and density. Transport properties of He and CH₄ under different forcefields namely; Compass and Polymer Consistent Force Field (PCFF) were studied at different temperatures. System size effects on the calculated excess chemical potentials and solubility, using the Widom insertion method, of both gases in amorphous PDMS were studied. The agreement between the measured and simulated diffusion coefficient (D) solubility (S) was acceptable. Transport of small molecules occurs by jumps between individual sections of the free volume (holes) through temporarily open channels. The dependence of diffusion on temperature shows an Arrhenius behavior and the associated activation energy was predicted.     

Crystal and molecular structure of zinc(II) di-n-propyldithiocarbamate complexes with 2,2-bipyridyl and 1,10-phenanthroline

The structure of Zn[S₂CN(n-C₃H₇)2]₂(2,2’-Bipy) and Zn[S₂CN(n-C₃H₇)₂]₂Phen was determined by X-ray diffraction analysis (CAD-4 diffractometer, MoK_α radiation) for the monoclinic (a = 9.646, b = 20.978, c = 14.555 å; Β = 94.95?; Z = 4; space group P2₁/n) and orthorhombic (a = 18.621, b = 14.701, c = 10.676 å; Z = 4; space group Aba2) crystals. The structures consist of discrete monomer molecules packed with the aid of S...H-C and C...H-C hydrogen bonds and van der Waals interactions.     

Membrane-water structural interactions in reverse osmosis transport

Reverse-osmotic water permeabilities, equilibrium water sorption levels, and rates of approach to sorption equilibrium were measured for a series of polymers, including hydroxyethyl methacrylate (HEMA), copolymers of HEMA and ethyl methacrylate (EMA), cellulose acetate, cellulose nitrate, and poly(urethans). Pronounced equilibrium solvent clustering behavior was observed for these systems as vapor saturation was approached in sorption experiments. However, clustering tendency was not found to be a function of total membrane water content at saturation but rather appears to be a function of the chemical nature of the polymer in question. Moreover, clustering of water molecules in (relatively) hydrophobic membranes resulted in low effective diffusivities (reverse osmotic permeability divided by equilibrium water content) whereas clustering in hydrophilic membranes led to higher effective water diffusivities. Clustering tendency was not as strong in the case of the weakly interacting membranes (i.e., the cellulose acetates). These conclusions were supported by theoretical diffusivity calculations. Predictions were based on analyses of transient sorption data, employing a dual-mode sorption model, and considering ordinary Fickian diffusion with simultaneous first-order reversible penetrant localization at water-binding sites in the polymer matrices. Means were found for correcting these diffusivity predictions to those values obtained experimentally under reverse osmosis conditions by accounting for the nonideality of the water flux under the latter conditions.     

Fabrication and electrochemical property modification of mixed matrix heterogeneous cation exchange membranes filled with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/PAA core-shell nanoparticles

In the current research, iron oxide nanoparticles were functionalized by acrylic acid polymerization. The Fe₃O₄/PAA core-shell nanoparticles were utilized for the modification of cation exchange membranes. Ion exchange membranes were prepared by solution casting technique using cation exchange resin powder as functional group agent and tetrahydrofuran as solvent. FTIR analysis proved the formation of PAA on nanoparticles. The SOM images also showed uniform particle distribution for the prepared membrane relatively. The membrane water content was declined from 30 to 17 % by increase of nanoparticle content ratio in membrane matrix. The contact angle measurements showed that membrane surface hydrophilicity was improved by utilizing of nanoparticles in the membrane matrix. The membrane potential, permselectivity, and transport number were improved initially by increase of nanoparticle concentration in the casting solution and then began to decrease by more additive concentration. Membrane ionic flux and permeability were enhanced initially by increase of nanoparticle loading ratio up to 0.5 %wt in membrane matrix and then showed decreasing trend by more increase of nanoparticle concentration from 0.5 to 4 %wt. Membrane areal electrical resistance was decreased sharply by utilization of nanoparticles up to 0.5 %wt in membrane matrix then began to increase by more additive concentration. The prepared membranes exhibited superior selectivity and low ionic flux at neutral condition compared to other acidic and alkaline environments.