The effect of morphology on the transport of dichloromethane in poly(aryl-ether-ether-ketone)

A study of the transport of the dichloromethane in neat poly(aryl-ether-ether-ketone) (PEEK) samples with thicknesses from 0.08 to 3.0 mm with different morphologies was conducted at 35°C. Both sorption and desorption of the solvent were studied. Thermal annealing was used to vary the sample morphology, and density measurements were used to determine the crystallinity of the samples. The equilibrium concentration of solvent and rate of solvent sorption were found to vary with sample morphology. The density of the dichloromethane when in the PEEK resin was found to be 1.65 g/cm³. Solvent desorption was independent of sample morphology or any previous sample treatment and depended only upon desorption temperature. Solvent sorption appears to alter the morphology of amorphous samples by increasing the crystallinity to about 20% after one sorption/desorption cycle. Small amounts of the solvent, less than 0.5 wt.%, remain trapped in fully desorbed samples. The micromorphology of solvent-induced crystallization appears to be different from that induced by thermal treatment.     

The solubility and diffusion of water in poly(aryl-ether-ether-ketone) (PEEK)

The transport properties of water in neat poly(aryl-ether-ether-ketone) (PEEK) coupons (2 to 6 mm thick) were investigated by gravimetric and mass spectrometric methods. The solubility of water increases from 0.44 wt.% at 35°C to 0.55 wt.% at 95°C; the temperature coefficient is 8 kJ/mol (1.9 kcal/mol). The diffusion processes for sorption, desorption, and resorption at 35°, 50°, 65°, 80°, and 95°C are, within experimental error, the same. The activation energy for diffusion is 42.7 kJ/mol (10.2 kcal/mol). The diffusion process is classical Case I Fickian in the temperature region investigated.     

Gas sorption,diffusion, and permeation in poly(dimethylsiloxane)

The permeability of poly(dimethylsiloxane) [PDMS] to H₂, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈, CF₄, C₂F₆, and C₃F₈, and solubility of these penetrants were determined as a function of pressure at 35 °C. Permeability coefficients of perfluorinated penetrants (CF₄, C₂F₆, and C₃F₈) are approximately an order of magnitude lower than those of their hydrocarbon analogs (CH₄, C₂H₆, and C₃H₈), and the perfluorocarbon permeabilities are significantly lower than even permanent gas permeability coefficients. This result is ascribed to very low perfluorocarbon solubilities in hydrocarbon‐based PDMS coupled with low diffusion coefficients relative to those of their hydrocarbon analogs. The perfluorocarbons are sparingly soluble in PDMS and exhibit linear sorption isotherms. The Flory–Huggins interaction parameters for perfluorocarbon penetrants are substantially greater than those of their hydrocarbon analogs, indicating less favorable energetics of mixing perfluorocarbons with PDMS. Based on the sorption results and conventional lattice solution theory with a coordination number of 10, the formation of a single C₃F₈/PDMS segment pair requires 460 J/mol more energy than the formation of a C₃H₈/PDMS pair. A breakdown in the geometric mean approximation of the interaction energy between fluorocarbons and hydrocarbons was observed. These results are consistent with the solubility behavior of hydrocarbon–fluorocarbon liquid mixtures and hydrocarbon and fluorocarbon gas solubility in hydrocarbon liquids. From the permeability and sorption data, diffusion coefficients were determined as a function of penetrant concentration. Perfluorocarbon diffusion coefficients are lower than those of their hydrocarbon analogs, consistent with the larger size of the fluorocarbons. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 415–434, 2000     

Thermal and other properties of complexes of Mn(II), Co(II) and Ni(II) with 2,2'-bipyridine and trichloroacetates

Complexes of the general formulae Mn(2-bpy)₂(CCl₃COO)₂, Co(2-bpy)₂(CCl₃COO)₂·H₂O and Ni(2-bpy)₂(CCl₃COO)₂·2H₂O (where: 2-bpy=2,2'-bipyridine) have been prepared and characterized by VIS and IR spectroscopy, conductivity and magnetic measurements. The thermal properties of complexes in the solid state were studied under non-isothermal conditions in air atmosphere. During heating the complexes decompose via different intermediate products to the oxides Mn₃O₄, CoO and NiO. A coupled TG-MS system was used to detection the principal volatile products of thermal decomposition and fragmentation processes of obtained compounds. The principal volatile products of thermal decomposition of complexes are: H₂O⁺, CO₂ ⁺, Cl₂ ⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Solubility Determination,Hansen Solubility Parameters and Thermodynamic Evaluation of Thymoquinone in (Isopropanol + Water) Compositions

This article studies the solubility, Hansen solubility parameters (HSPs), and thermodynamic behavior of a naturally-derived bioactive thymoquinone (TQ) in different binary combinations of isopropanol (IPA) and water (H₂O). The mole fraction solubilities (x₃) of TQ in various (IPA + H₂O) compositions are measured at 298.2–318.2 K and 0.1 MPa. The HSPs of TQ, neat IPA, neat H₂O, and binary (IPA + H₂O) compositions free of TQ are also determined. The x₃ data of TQ are regressed by van’t Hoff, Apelblat, Yalkowsky–Roseman, Buchowski–Ksiazczak λh, Jouyban–Acree, and Jouyban–Acree–van’t Hoff models. The maximum and minimum x₃ values of TQ are recorded in neat IPA (7.63 × 10⁻² at 318.2 K) and neat H₂O (8.25 × 10⁻⁵ at 298.2 K), respectively. The solubility of TQ is recorded as increasing with the rise in temperature and IPA mass fraction in all (IPA + H₂O) mixtures, including pure IPA and pure H₂O. The HSP of TQ is similar to that of pure IPA, suggesting the great potential of IPA in TQ solubilization. The maximum molecular solute-solvent interactions are found in TQ-IPA compared to TQ-H₂O. A thermodynamic study indicates an endothermic and entropy-driven dissolution of TQ in all (IPA + H₂O) mixtures, including pure IPA and pure H₂O.     

Thermal and Other Properties of New 4,4'-bipyridine-trichloroacetato Complexes of Mn(II), Ni(II) and Zn(II)

New mixed-ligand complexes of general formulae Mn(4-bpy)(CCl₃COO)₂⋅H₂O, Ni(4-bpy)₂(CCl³COO)₂⋅2H²O and Zn(4-bpy)₂(CCl₃COO)₂⋅2H²O (where 4-bpy=4,4’-bipyridine) were obtained and characterized. The IR spectra, conductivity measurements and other physical properties of these compounds were discussed. The central atoms M(II) form coordinate bonds with title ligands. The thermal behaviour of the synthesized complexes was studied in air. During heating the complexes decompose via different intermediate products to Mn₃O₄, NiO and ZnO; partial volatilization of ZnCl₂was observed. A coupled TG-MS system was used to the analysis of the principal volatile thermal decomposition products of Mn(II) and Ni(II) complexes. The principal volatile mass fragments correspond to: H₂O⁺, OH⁺, CO⁺ ₂, HCl⁺, Cl⁺ ₂, CCl⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Solubility and transport of water vapor in some 6FDA-based polyimides

Permeability, diffusion, and solubility coefficients for H₂O vapor in four different 6FDA-based polyimides were determined at temperatures between 25 and 45°C and over a wide range of relative humidities. The solubility of H₂O vapor in some of the polyimides studied can be described by the “dual-mode sorption” model whereas in other polyimides it is represented by the Flory-Huggins equation, which suggests that the latter polymers are plasticized by H₂O. The solubility of H₂O vapor in the polyimides decreases as the temperature is raised and increases with increasing polarity of the polymer. The diffusion coefficients for H₂O in the polyimides studied either increase or pass through a weak maximum with increasing H₂O activity, or concentration in the polymers. The latter behavior is probably due to a clustering of H₂O molecules in the polyimides at higher H₂O activities or concentrations. The diffusion coefficients for H₂O decrease as the chain-packing density of the polyimides increases. The permeability coefficients for H₂O vapor in 6FDA-based polyimide membranes either increase slightly or are constant as the H₂O activity is increased. The experimental values of the permeability coefficients are consistent with the values determined from diffusion and solubility coefficients. The permeability of the polyimides to H₂O vapor appears to be controlled by the solubility of H₂O in the polymers. The polyimides studied exhibit a very high selectivity for H₂O vapor relative to CH_4, and therefore are potentially useful membrane materials for the dehydration of natural gas. ©1995 John Wiley & Sons, Inc.     

Ethylbenzene solubility,diffusivity, and permeability in poly(dimethylsiloxane)

The pure‐gas sorption, diffusion, and permeation properties of ethylbenzene in poly(dimethylsiloxane) (PDMS) are reported at 35, 45, and 55 °C and at pressures ranging from 0 to 4.4 cmHg. Additionally, mixed‐gas ethylbenzene/N₂ permeability properties at 35 °C, a total feed pressure of 10 atm, and a permeate pressure of 1 atm are reported. Ethylbenzene solubility increases with increasing penetrant relative pressure and can be described by the Flory–Rehner model with an interaction parameter of 0.24 ± 0.02. At a fixed relative pressure, ethylbenzene solubility decreases with increasing temperature, and the enthalpy of sorption is −41.4 ± 0.3 kJ/mol, which is independent of ethylbenzene concentration and essentially equal to the enthalpy of condensation of pure ethylbenzene. Ethylbenzene diffusion coefficients decrease with increasing concentration at 35 °C. The activation energy of ethylbenzene diffusion in PDMS at infinite dilution is 49 ± 6 kJ/mol. The ethylbenzene activation energies of permeation decrease from near 0 to −34 ± 7 kJ/mol as concentration increases, whereas the activation energy of permeation for pure N₂ is 8 ± 2 kJ/mol. At 35 °C, ethylbenzene and N₂ permeability coefficients determined from pure‐gas permeation experiments are similar to those obtained from mixed‐gas permeation experiments, and ethylbenzene/N₂ selectivity values as high as 800 were observed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1461–1473, 2000     

Gas permeability and hydrocarbon solubility of poly[1‐phenyl‐2‐[p‐(triisopropylsilyl)phenyl]acetylene]

The effects of film thickness, physical aging, and methanol conditioning on the solubility and transport properties of glassy poly[1‐phenyl‐2‐[p‐(triisopropylsilyl) phenyl]acetylene] are reported at 35 °C. In general, the gas permeability coefficients are very high, and this polymer is more permeable to larger hydrocarbons (e.g., C₃H₈ and C₄H₁₀) than to light gases such as H₂. The gas permeability and solubility coefficients are higher in as‐cast, unaged films than in as‐cast films aged at ambient conditions and increase to a maximum in both unaged and aged as‐cast films after methanol conditioning. For example, the oxygen permeability of a 20‐μm‐thick as‐cast film is initially 100 barrer and decreases to 40 barrer after aging for 1 week at ambient conditions. After methanol treatment, the oxygen permeabilities of unaged and aged films increase to 430 and 460 barrer, respectively. Thicker as‐cast films have higher gas permeabilities than thinner as‐cast films. Propane and n‐butane sorption isotherms suggest significant changes in the nonequilibrium excess free volume in these glassy polymer films due to processing history. For example, the nonequilibrium excess free volume estimated from the sorption data is similar for as‐cast, unaged samples and methanol‐conditioned samples; it is 100% higher in methanol‐conditioned films than in aged, as‐cast films. The sensitivity of permeability to processing history may be due in large measure to the influence of processing history on nonequilibrium excess free volume and free volume distribution. The propane and n‐butane diffusion coefficients are also sensitive to film processing history, presumably because of the dependence of diffusivity on free volume and free volume distribution. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1474–1484, 2000     

Synthesis,crystal structure and thermal stability of new copper(II) trichloroacetate complexes

We have synthesized two novel complexes of copper(II) trichloro acetate, Cu₂(CCl₃COO)₃(OH)(H₂O)₄·H₂O and Cu(CCl₃COO)₂(MeCN), and determined their crystal structures and thermal stability. While the complex with acetonitrile has a discrete binuclear paddle-wheel structure, typical of copper carboxylates, the aqua-hydroxo complex belongs to a novel unique chain–molecular type of basic copper complexes.     

Transport behavior of carbon disulfide into poly aryl ether ether ketone

The sorption/desorption of carbon disulfide into/from PEEK as a function of crystallinity and temperature was investigated. The sorption curves of carbon disulfide into PEEK show only two major regions: (a) an increase of penetrant weight with time, and (b) a limiting equilibrium value (solubility). This is in contrast to the sorption of toluene into PEEK which shows three regions. The solubility of carbon disulfide decreases with increasing crystallinity, but temperature has little effect on the solubility in the temperature range of 25–40°C. An acceleration in penetration rate at the later stage of diffusion is observed for PEEK films whose crystallinity is greater than 13.4%, suggesting Supercase II diffusion. Carbon disulfide can be desorbed completely from PEEK in contrast to other fluids, such as toluene or methylene chloride, which are difficult to desorb. The normalized weight loss of carbon disulfide during desorption is an exponential function of square-root time. Solvent-induced crystallization was observed. Crystallinity was estimated from both the measured density and microhardness of the desorbed polymer and polymer which had undergone a sorption/desorption/resorption/desorption cycle. © 1996 John Wiley & Sons, Inc.     

Correlation amongst gas barrier behaviour,temperature and thickness in BOPP films for food packaging usage: A lab-scale testing experience

Permeability of gases in polymers depends strongly upon the polymer structure, the gas type, as well as the conditions of temperature and film thickness. The in-use temperature and thickness of the polymer membrane can play the most important role on preservation and prolongation of food shelf-life. In this work the gas transmission parameters of six Bi-axially Oriented Polypropylene (BOPP) films were investigated as a function of temperature, gas type and thickness. O₂, CO₂, N₂, N₂O, C₂H₄, Air (79%N₂/21%O₂) and Modified Atmosphere (MA) of 79%N₂O/21%O₂ were used as test gas. In order to understand the kinetic of the process, by the activation energy determination, samples were tested at a different temperature, from 10 °C to 40 °C. Gas Transmission Rate (GTR), solubility (S) and diffusion (D) relationship was investigated. The gas/thickness/temperature correlation was reflected in the obtained perm-selectivity ratios and a good linear correlation was found only at 23 °C. Deviations recorded were attributed to temperature fluctuations. Gas transmission process follows the Arrhenius model while the solubility/diffusion process shows consistent deviation, correlated to the temperature and the thickness of the film. By Differential Scanning Calorimetry (DSC) a different crystallinity percentage was recorded, whose influence was evidenced only in the sorption/diffusion processes. The melting temperature remained unchanged. FT-IR Spectroscopy was also carried out to confirm the morphology.     

New 2,2'-bipyridine-chloroacetato complexes of transition metals(II)

Summary The new mixed-ligand complexes of d-electron metals (M(II)=Mn, Ni, Cu) with 2,2'-bipyridine (2-bpy) and mono- or dichloroacetates were prepared as crystalline solids. The general formulae of the synthetized complexes are: Cu(2-bpy)₂(CClH₂COO)₂·2H₂O, Mn(2-bpy)₂(CCl₂HCOO)₂, M(2-bpy)₂(CCl₂HCOO)₂·2H₂O (M(II)=Ni, Cu). The compounds were characterized by chemical analysis, IR and VIS spectroscopy. Their magnetic, molar conductivity and thermal properties also were studied. During heating in air complexes decompose via different intermediate products to metal oxides. A coupled TG-MS system was used to analyse the principal volatile thermal decomposition (or fragmentation) products of 2,2'-bipyridine-chloroacetato complexes.     

Electrocarboxylation of CCI<Subscript>4</Subscript> in MeCN during electrolysis with the sacrificial Zn anode

The regularities of galvanostatic electrocarboxylation of CCl₄ in Alk₄NBr/MeCN in an undivided cell with sacrificial Zn anode were studied. The major product of the electrolysis is zinc trichloroacetate, which is formed as a result of the reaction of the cathode-generated CCl₃- anion with CO₂. The further trichloroacetate reduction is prevented by cathode passivation. Therefore, small amounts of zinc dichloro- and monochloroacetates are formed due to the chemical reduction of zinc trichloroacetate with Zn⁰ rather than the cathodic reduction. Zero-valence zinc is formed in minor amounts when Zn²⁺ ions are discharged at the cathode surface because of the low solubility of ZnBr₂ in MeCN. The treatment of (Cl₃CCOO)₂Zn with H₂SO₄ in MeOH gives Cl₃CCO₂Me in 11% yield based on the starting CCl₄.     

Synthesis and Properties of Lead(II) 1-Hydroxyethane-1,1-diphosphonate(2-) Monohydrate

Conditions for isolation of a 1-hydroxyethane-1,1-diphosphonic acid (H₄L) complex of the composition PbH₂L·H₂O from aqueous solutions of various composition are studied. The X-ray analysis of the resulting polycrystalline sample showed that it is single-phase. The IR spectrum is presented, and the solubility and thermal transformations of the sample are studied.     

Preparation and characterization of a composite PDMS membrane on CA support

Polydimethylsiloxane (PDMS) is the most commonly used membrane material for the separation of condensable vapors from lighter gases. In this study, a composite PDMS membrane was prepared and its gas permeation properties were investigated at various upstream pressures. A microporous cellulose acetate (CA) support was initially prepared and characterized. Then, PDMS solution, containing crosslinker and catalyst, was cast over the support. Sorption and permeation of C₃H₈, CO₂, CH₄, and H₂ in the prepared composite membrane were measured. Using sorption and permeation data of gases, diffusion coefficients were calculated based on solution‐diffusion mechanism. Similar to other rubbery membranes, the prepared PDMS membrane advantageously exhibited less resistance to permeation of heavier gases, such as C₃H₈, compared to the lighter ones, such as CO₂, CH₄, and H₂. This result was attributed to the very high solubility of larger gas molecules in the hydrocarbon‐based PDMS membrane in spite of their lower diffusion coefficients relative to smaller molecules. Increasing feed pressure increased permeability, solubility, and diffusion coefficients of the heavier gases while decreased those of the lighter ones. At constant temperature (25°C), empirical linear relations were proposed for permeability, solubility, and diffusion coefficients as a function of transmembrane pressure. C₃H₈/gas solubility, diffusivity, and overall selectivities were found to increase with increasing feed pressure. Ideal selectivity values of 9, 30, and 82 for C₃H₈ over CO₂, CH₄, and H₂, respectively, at an upstream pressure of 8 atm, confirmed the outstanding separation performance of the prepared membrane. Copyright © 2009 John Wiley & Sons, Ltd.     

Solid state and solution study of some phosphoramidate derivatives containing the P(O)NHC(O) bifunctional group: Crystal structures of CCl2HC(O)NHP(O)(NCH3(CH2C6H5))2, p-ClC6H4C(O)NHP(O)(NCH3(CH2C6H5))2, CCl2HC(O)NHP(O)(N(CH2C6H5)2)2 and p-BrC6H4C(O)NHP(O)(N(CH2C6H5)2)2

Synthetic methods for several novel phosphoramidate compounds containing the P(O)NHC(O) bifunctional group were developed. These compounds with the general formula R₁C(O)NHP(O)(N(R₂)(CH₂C₆H₅))₂, where R₁ = CCl₂H, p-ClC₆H₄, p-BrC₆H₄, o-FC₆H₄ and R₂ = hydrogen, methyl, benzyl, were characterized by several spectroscopic methods and analytical techniques. The effects of phosphorus substituents on the rotation rate around the P–N_amine bond were also investigated. ¹H NMR study of the synthesized compounds demonstrated that the presence of bulky groups attached to the phosphorus center and electron withdrawing groups in the amide moiety lead to large chemical-shift non-equivalence (Δδ_H) of diastereotopic methylene protons. The crystal structures of CCl₂HC(O)NHP(O)(NCH₃(CH₂C₆H₅))₂, p-ClC₆H₄C(O)NHP(O)(NCH₃(CH₂C₆H₅))₂, CCl₂HC(O)NHP(O)(N(CH₂C₆H₅)₂)₂ and p-BrC₆H₄C(O)NHP(O)(N(CH₂C₆H₅)₂)₂ were determined by X-ray crystallography using single crystals. The coordination around the phosphorus center in these compounds is best described as distorted tetrahedral and the P(O) and C(O) groups are anti with respect to each other. In the compound Br-C₆H₄C(O)NHP(O)(N(CH₂C₆H₅)₂)₂ (with two independent molecules in the unit cell), two conformers are connected to each other via two different N–H?O hydrogen bonds forming a non-centrosymmetric dimer. In the crystalline lattice of other compounds, the molecules form centrosymmetric dimers via pairs of same N–H?O hydrogen bonds. The structure of CCl₂HC(O)NHP(O)(N(CH₂C₆H₅)₂)₂ reveals an unusual intramolecular interaction between the oxygen of CO group and amine nitrogen.     

Thermal conductivity of poly(ether ether ketone) and its short-fiber composites

The effects of crystallinity, orientation, and short-fiber filler on the thermal diffusivity D and thermal conductivity K of poly (ether ether ketone) (PEEK) have been studied. Below the glass transition, D increases by less than 10% as the crystallinity increases from 0 to 0.3. For amorphous PEEK, there is an abrupt drop in D at the glass transition (T_g ? 420 K). The drop is less prominent for the 30% crystalline sample and occurs at 20 K higher. At a draw ratio of 2.5, the axial thermal conductivity is 2.3 times higher while the transverse thermal conductivity is 30% lower than that of the unoriented material. For an injection-molded bar of carbon fiber reinforced PEEK, the variation of D with position along the width or thickness direction is found to correlate well with the fiber orientation. By regarding the injection-molded bar as a multidirectional laminate comprising a large number of unidirectional plies, the thermal conductivities along the longitudinal and transverse direction are calculated and found to agree closely with the experimental data. © 1994 John Wiley & Sons, Inc.     

A New Oscillating Reaction of the Belousov-Zhabotinskii-type with a Macrocyclic Copper(II) Complex as Catalyst

The reaction of bromate ion with malic acid in aqueous H₂SO₄ catalyzed by a tetraazamacrocyclic copper(II) complex exhibits oscillatory behavior. This complex contains an unsaturated macrocyclic ligand, 5,7,7,12,14,14-hexemethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The reactions were monitored both spectrophotometrically and potentiometrically. It was found that the oscillation period (tp) is dependent on the initial concentrations of malic acid or H₂SO₄ but is independent of the initial concentrations of NaBrO₃. The experimental results indicate that acrylonitrile, H₂O₂, vitamin C, glucose or CCl₄ present in the system can inhibit the oscillations. A tentative mechanism is proposed.     

Solvent extraction behaviour of iodine and bromine in aqueous-organic systems,analogy with radioactive decay

The extraction of iodine and bromine under various conditions from their saturated aqueous solutions by CCl₄, C₆H₆ and o-xylene has been studied. The data obtained from the experiments carried out at various temperatures, for H₂O(I₂)−CCl₄ and H₂O(I₂)−C₆H₆ systems, exhibit an Arrhenius behaviour. The overall activation energy calculated for the extraction in the H₂O(I₂)−CCl₄ system, 650±50 cal·mol⁻¹ is lower than that of H₂O(I₂)−C₆H₆, 3600±300 cal·mol⁻¹. The use of the solubility parameter for the interpretation of the data in the extraction of iodine is investigated. The data obtained in multiple extractions are treated by using the analogy between extraction and radioactive decay. The half number of extraction for each system is determined. The complex curves obtained in the H₂O(I₂)−CCl₄ and H₂O(I₂) −Br₂)−CCl₄ systems are resolved into two components.