Oxygen selective ceramic hollow fiber membranes for partial oxidation of methane

A BaCo_xFe_yZr_zO_3?δ (BCFZ) perovskite hollow fiber membrane was used to construct reactors for the partial oxidation of methane (POM) to syngas. The performance of the BCFZ fibers in the POM was studied (i) without any catalyst, (ii) with catalyst‐coated fibers, and (iii) with catalyst packed around the fibers. In addition to the performance in the POM, the stability of the BCFZ hollow fiber membranes was investigated for the different catalyst arrangements. Best stability of the BCFZ hollow fiber membrane reactor in the POM could be obtained if the reforming catalyst is placed behind the oxygen permeation zone. It was found that a direct contact of the catalyst and the fiber must be avoided which could be achieved by coating the fiber with a gold film. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Partial oxidation of methane in hollow‐fiber membrane reactors based on alkaline‐earth metal‐free CO2‐tolerant oxide

The U‐shaped alkaline‐earth metal‐free CO₂‐stable oxide hollow‐fiber membranes based on (Pr_0.9La_0.1)₂(Ni_0.74Cu_0.21Ga_0.05)O_4+δ (PLNCG) are prepared by a phase‐inversion spinning process and applied successfully in the partial oxidation of methane (POM) to syngas. The effects of temperature, CH₄ concentration and flow rate of the feed air on CH₄ conversion, CO selectivity, H₂/CO ratio, and oxygen permeation flux through the PLNCG hollow‐fiber membrane are investigated in detail. The oxygen permeation flux arrives at approximately 10.5 mL/min cm² and the CO selectivity is higher than 99.5% with a CH₄ conversion of 97.0% and a H₂/CO ratio of 1.8 during 140 h steady operation. The spent hollow‐fiber membrane still maintains a dense microstructure and the Ruddlesden‐Popper K₂NiF₄‐type structure, which indicates that the U‐shaped alkaline‐earth metal‐free CO₂‐tolerant PLNCG hollow‐fiber membrane reactor can be steadily operated for POM to syngas with good performance. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3587–3595, 2014     

A robust mixed‐conducting multichannel hollow fiber membrane reactor

To accelerate the commercial application of mixed‐conducting membrane reactor for catalytic reaction processes, a robust mixed‐conducting multichannel hollow fiber (MCMHF) membrane reactor was constructed and characterized in this work. The MCMHF membrane based on reduction‐tolerant and CO₂‐stable SrFe_0.8Nb_0.2O_3‐δ (SFN) oxide not only possesses a good mechanical strength but also has a high oxygen permeation flux under air/He gradient, which is about four times that of SFN disk membrane. When partial oxidation of methane (POM) was performed in the MCMHF membrane reactor, excellent reaction performance (oxygen flux of 19.2 mL min^?1 cm^?2, hydrogen production rate of 54.7 mL min^?1 cm^?2, methane conversion of 94.6% and the CO selectivity of 99%) was achieved at 1173 K. And also, the MCMHF membrane reactor for POM reaction was operated stably for 120 h without obvious degradation of reaction performance. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2592–2599, 2015     

Oxygen barrier,free volume,and blending properties of fully bio-based polyamide 11/poly(vinyl alcohol) blends

Fully bio-based polyamide 11 (PA11) was melt-blended with poly(vinyl alcohol) (PVA) with varying degrees of polymerization (DP) to prepare PA11_xPVA^z_y. The PA11_xPVA^z_y films demonstrated the lowest oxygen transmission rates (OTR) and free volume characteristics, when PVA contents of each PA11_xPVA^z_y series reached a corresponding critical concentration. The minimum OTR and free volume characteristics obtained for the optimal PA11_xPVA^z_y films reduced significantly with decreasing PVA DPs. The OTR of the optimal PA11_xPVA^z_y blown film was 1.07 cm³ m⁻² day⁻¹ atm⁻¹, which is near to that of the ethylene-vinyl alcohol copolymer high-barrier polymer. The results of dynamical, mechanical, and other experimental characterizations demonstrated that PA11 and PVA are compatible to some extent when PVA concentrations are less-than or equal to the respective critical values. The enhanced oxygen permeation resistance and free volume characteristics for optimal PA11_xPVA^z_y films are at least partly ascribed to the improved hydrogen-bonded molecular interactions between PA11 CO groups and PVA O─H groups. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48562.     

La0.6Sr0.4Co0.8Ga0.2O3‐δ (LSCG) hollow fiber membrane reactor: Partial oxidation of methane at medium temperature

In this study, La_0.6Sr_0.4Co_0.8Ga_0.2O_3‐δ (LSCG) hollow fiber membrane reactor was integrated with Ni/LaAlO₃‐Al₂O₃ catalyst for the catalytic partial oxidation of methane (POM) reaction. The process was successfully carried out in the medium temperature range (600–800°C) for reaction of blank POM with bare membrane, catalytic POM reaction and swept with H₂:CO gas mixture. For the catalytic POM reaction, enhancement in selectivity to H₂ and CO is obtained between 650–750°C when O₂:CH₄ <1. High CH₄ conversion of 97% is achieved at 750°C with corresponding H₂ and CO selectivity of about 74 and 91%. The oxygen flux of the membranes also increased with the increase in oxygen partial pressure gradient across the membrane. The postreacted membranes were tested via XRD and FESEM‐EDX for their crystallinity and surface morphology. XPS analysis was further used to investigate the O1s, Co 2p and Sr 3d binding energies of the segregated elements from the reducing reaction environment. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3874–3885, 2013     

Phase Diagram and Enhanced Piezoelectric Response of Lead‐Free BaTiO3–CaTiO3–BaHfO3 System

Three composition groups in the BaTiO₃–CaTiO₃–BaHfO₃ ternary system, (1 ? x)Ba(Hf_yTi_1?y)O₃–x(Ba_1?zCa_z)TiO₃ (abbreviated as BH_yT–xBC_zT with x = 0–1.0, y = 0.16, z = 0.20; x = 0–1.0, y = 0.16, z = 0.30; x = 0–1.0, y = 0.20, z = 0.30, respectively), have been designed for investigating the variation of the intermediate O‐phase region and its effect on the electrical properties. The temperature‐composition phase diagram of each group has been proposed based on the X‐ray diffraction patterns and the temperature‐dependent dielectric behaviors. The enhanced piezoelectric properties are achieved in the O–T phase boundary compositions of the three groups, which are BH_0.16T–0.58BC_0.20T, BH_0.16T–0.48BC_0.30T and BH_0.20T–0.53BC_0.30T, respectively. Piezoelectric coefficient d₃₃ of 448 pC/N is obtained in BH_0.20T–0.53BC_0.30T, which is higher than those of the other two phase boundary compositions. The O‐phase zone in BH_0.20T–xBC_0.30T is narrower than those in the BH_0.16T–xBC_0.20T and BH_0.16T–xBC_0.30T. In spite of its small O‐phase volume occupancy, the O‐phase plays a key role in the properties of the system. Our work confirms that the enhancement in piezoelectric properties is not only related to the O–T phase boundary near room temperature (RT), but also related to the shift of T_R‐O toward RT. In addition, a quantitative relation between the phase boundary composition and atomic mole ratio of Hf to Ca (R_m) is proposed, which the R_m value corresponding to the phase boundary is about 0.58. The results clearly demonstrate that in this system high piezoelectric properties are achieved by tuning the specific R_m value. Such a work may provide new clues for designing lead‐free piezoelectric materials with enhanced piezoelectric property.     

Evaluation of RuxWySez Catalyst as a Cathode Electrode in a Polymer Electrolyte Membrane Fuel Cell

The oxygen reduction reaction (ORR) on Ru_xW_ySe_z is of great importance in the development of a novel cathode electrode in a polymer electrolyte membrane fuel cell (PEMFC) technology. The Ru_xW_ySe_z electrocatalyst was synthesised in an organic solvent for 3 h. The powder was characterised by transmission electron microscopy (TEM), and powder X‐ray diffraction (XRD). The electrocatalyst consisted of agglomerates of nanometric size (∼50–150 nm) particles. In the electrochemical studies, rotating disc electrode (RDE) and rotating ring‐disc electrode (RRDE) techniques were used to determine the oxygen reduction kinetics in 0.5 M H₂SO₄. The kinetic studies include the determination of Tafel slope (112 mV dec^–1), exchange current density at 25 °C (1.48 × 10^–4 mA cm^–2) and the apparent activation energy of the oxygen reaction (52.1 � 0.4 kJ mol^–1). Analysis of the data shows a multi‐electron charge transfer process to water formation, with 2% H₂O₂ production. A single PEMFC with the Ru_xW_ySe_z cathode catalysts generated a power density of 180 mW cm^–2. Performance achieved with a loading of 1.4 mg cm^–2 of a 40 wt% Ru_xW_ySe_z and 60 wt% carbon Vulcan (i.e. 0.56 mg cm^–2 of pure Ru_xW_ySe_z). Single PEMFC working was obtained with hydrogen and oxygen at 80 °C with 30 psi.     

New sulfur adsorbents derived from layered double hydroxides: I: Synthesis and COS adsorption

Mixed oxides, prepared via the thermal decomposition of layered double hydroxides (LDHs), were screened gravimetrically for their ability to adsorb carbonyl sulfide (COS). Based on promising results obtained for Ni/Mg/Al, Ni/Mg/Fe and Co/Mg/Al mixed oxides, a study was undertaken to optimize the composition of these materials for COS adsorption. To investigate the effect of the M(II):M(III) ratio, LDHs of the type [M_zMg_yAl_x(OH)₂](CO₃)_x/2·0.5H₂O (where M = Ni or Co, and x + y + z = 1) were prepared at values of x corresponding to 0.33 and 0.20. Simultaneously, the elemental ratio of transition metal to magnesium (z/y) was varied. Mixed oxides obtained from the resulting LDHs were tested in fixed bed mode with a feed of 100 ppm COS in N₂ to determine breakthrough capacity. In general Ni/Mg/Al mixed oxides showed the best performance, a composition with Ni/Mg/Al = 0.32/0.48/0.20 showing the best adsorption capacity. Treatment of the spent adsorbent under an atmosphere of 5% H₂ in N₂ at 450 °C was found to provide an effective means of restoring the adsorption capacity over two cycles of adsorption and regeneration, although after three such cycles, adsorption capacity decreased.     

Y3Al5O12–SiO2 Glasses: Structure and Polyamorphism

Aerodynamic levitation and CO₂ laser melting have been used to synthesize the yttrium aluminosilicate glasses zY₂O₃–yAl₂O₃–xSiO₂ with z/y = 3/5 corresponding to the YAG (Y₃Al₅O₁₂) composition and x between ~5 and ~45 mol%. The low‐ and high‐density (LDA inclusion and HDA matrix) polyamorphic phases in glasses with less than ~14 mol% SiO₂ were identified with backscattering electron imaging. Polarized and depolarized Raman spectra show the formation of various Qⁿ SiO₄ species whose relative populations change smoothly as the SiO₂ content is altered. The AlOs (s = 4–6) and YOz (z = 6–9) polyhedra formed in the YAG glass are preserved upon silica additions while the terminal oxygens of the Q²AlO₄ tetrahedra are gradually bridged to the Qⁿ‐SiO₄ species. The low‐frequency Boson Peak overlaps with the vibrational spectrum and its maximum is redshifted with increasing silica content. Micro‐Raman spectra measured for the LDA and HDA amorphous phases are found to be similar to the spectra of the bulk glass indicating common structural characteristics. The stability of the LDA phase against crystallization appears to be lower than that of the HDA phase. The crystallinity on certain inclusions consisted of YAG microcrystals and a new unidentified microcrystalline phase within Y₄Al_2(1?x)Si_2xO_(9+x) solid solution.     

Eu‐Doped β‐SiAlON Phosphors: Template‐Assistant Low Temperature Synthesis,Dual Band Emission,and High‐Thermal Stability

A hard template route has been successfully developed for synthesis of β‐SiAlON:Eu phosphors at low temperatures. The synthesis utilizes mesoporous silica (SBA‐15) skeleton as an active Si source, combined with the carbothermal reduction and nitridation method. It has been shown that the additional driving force from high surface area and porosity of SBA‐15 enables β‐SiAlON:Eu (with compositions of Si_6?zAl_z?xO_z+xN_8?z?x: xEu, x = 0.010–0.200 and z = 1.000) phosphors to be formed as a dominant phase at low temperature of 1400°C. The resultant β‐SiAlON:Eu phosphor powders exhibit a typical rod‐like morphology and a well dispersed state. By tailoring the Eu²⁺ concentration in the phosphors, a continuous change in emission band can be realized, that is a blue emission dominated for low Eu²⁺ concentrations and a green emission dominated for high Eu²⁺ doping concentrations. Furthermore, the resultant phosphors exhibit a small thermal quenching up to high temperature of 250°C. Therefore, the developed method is beneficial to synthesize LED phosphors of oxynitride systems at lower temperatures.     

A Combined Experimental and Computational Thermodynamic Investigation of the U–Th–O System

The thermodynamics of the U–Th–O system have been assessed using the Calphad method. The compound energy formalism (CEF) and a partially ionic two‐sublattice liquid model (TSLM) were used for the fluorite U_1–yTh_yO_2±x, γ‐(U,Th)₄O₉, and the U–Th–O melt. The O₂ activity of fluorite U_1–yTh_yO_2±x with temperature and composition was determined by thermogravimetric analysis. Thermodynamic studies for the Th–O binary and U–Th–O ternary available in the open literature were critically reviewed. A self‐consistent data set was selected and compiled with the equilibrium oxygen pressures determined by thermogravimetry in order to optimize the adjustable parameters of models selected to represent the phases in the Th–O and U–Th–O systems.     

Sonochemical synthesis of mesoporous GdxZryTizCe1−x–y–zO2 solid solution

Gd_xZr_yTi_zCe_{1−x–y–z}O₂ (x+y+z≤0.3) solid solutions with a crystallite size of 5–10 nm have been prepared by the sonochemical method from inorganic salts without any additives. In all cases, ceria based materials exhibited a mesoporous structure with polymodal pore size distribution with diameter of 2–10 nm. It was shown that crystallite size and specific surface area remained practically unchanged while changing the dopant concentration.     

Oxygen induced direct hydrogenation of CO on Ni(100) surface

A trace amount of oxygen in H₂ promotes a new type of direct hydrogenation reaction of adsorbed CO on Ni(100) surface. The formation of H_xCO_y was suggested by high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). HREEL spectra showed the formation of surface hydroxyl (OH) and the C-H bonds of H_iCO_y species but no carbonyl (C=O) loss peak was detected although thermal desorption yielded large amount of CO. The H _x CO _y undergoes the decomposition at 400–450 K on the hex-OH Ni(100) surface, which yielded CO, CO₂, H₂ and H₂CO. It was confirmed that no C-H bond formation occurs on c(2 × 2)-O, p(2 × 2)-O Ni(100) and hex-OH Ni(100) as well as on clean Ni(100) surfaces. This fact indicates that the gas phase oxygen may induce the direct hydrogenation of CO to form H _x CO _y , which is analogous to the hydrogenation of O to form hex-OH onNi(100).     

Open-circuit-potentials of gas/electrode/YSZ boundary versus molten carbonate reference electrode at medium temperatures: II. Potential response of Au, Pt and Ni-cermet electrodes in CH4 + O2 and H2 + O2 gas mixtures

Values of open-circuit-potentials (OCP) have been determined for pairs of electrodes: Au and Pt, Ni-Ce_0.8Sm_0.2O_1.9 cermet and Au, Pt and Sm_0.5Sr_0.5CoO₃ composite at the YSZ electrolyte, in the uniform atmospheres of xCH₄ + yO₂ + (1 − x − y)Ar gas mixtures with variable x and y coefficients, at 600 °C. The determined dependencies of OCP values on the initial gas mixture compositions have been compared with the respective dependencies calculated for equilibrium or quasi-equilibrium compositions of these gas mixtures. The OCP values for the pair of Pt and Au electrodes have been measured also in the xH₂ + yO₂ + (1 − x − y)Ar uniform gas mixtures but no distinct difference of the OCP values has been observed in this atmosphere. For some pairs of electrodes investigated in xCH₄ + yO₂ + (1 − x − y)Ar atmospheres the measured OCP values have shown differences up to ca 0.9-1.0 V. These differences were stable within large range of compositions of this gas mixture. Within this gas composition range one of the electrodes conserves the potential of oxygen electrode determined by oxygen partial pressure in the initial gas mixture and is insensitive to reaction occurring in the gas phase. These results are discussed on the basis of equilibria or some quasi-equilibria, that establish in the C-H-O gas mixture and the solid carbon deposition is considered. For a given pair of dissimilar electrodes, their selective sensibility to the electrochemical process of oxygen electrode has been confirmed. Within large range of gas mixture concentrations, in the Pt-Au electrode pair Au has shown behavior of the oxygen electrode, whereas the OCP values of the Pt electrode are within the range of hydrogen electrode, also at gas compositions corresponding to the solid carbon stability. With this pair the OCP differences of ca. 600 mV have been obtained. Among three electrodes studied the cermet Ni-Ce_0.8Sm_0.2O_1.9 electrode shows the best electrocatalytic properties resulting in the OCP values following exactly the respective equilibrium dependence. In the pair Ni-Ce_0.8Sm_0.2O_1.9 and Au a stable potential difference of ca. 900 mV have been established. Unexpectedly, Pt electrode in the pair with the Sm_0.5Sr_0.5CoO₃ composite electrode plays role of the oxygen electrode quite insensitive to other components of the equilibrated initial gas mixture. This surprising fact seems indicate that in conditions of the experiments performed the electrocatalytic behavior of the electrode depends not only of the material of this electrode but also on the properties of the second electrode in the given pairs of electrodes.     

Realizing the invariant electrostrain response and low hysteresis via multicomponent coordination in Pb-based ceramics

High-performance piezoelectric materials are essential in many piezoelectric devices. However, the composition of piezoelectric materials usually has a great influence on their performance. In this work, xBi(Mg_1/2Ti_1/2)O₃–yPbZrO₃–zPbTiO₃ (xBMT–yPZ–zPT; 0.2 ≤ x ≤ 0.4, 0.25 ≤ y ≤ 0.4, and 0.35 ≤ z ≤ 0.4) ternary ceramics with different compositions were synthesized and it was found that the strain response was not sensitive to the composition. The crystal structure, strain response, ferroelectric properties, and temperature stability of xBMT–yPZ–zPT ceramics were investigated in detail. X-ray diffraction patterns show that all the as-prepared xBMT–yPZ–zPT ceramics with x = 0.2, 0.3, 0.4, and 0.5 possess a perovskite structure. Under an external electric field of 6 kV mm⁻¹, the strain values of xBMT–yPZ–zPT ternary ceramics with x = 0.2, 0.3, 0.4, and 0.5 were 0.30%, 0.31%, 0.30%, and 0.27%, respectively. In addition, the strain hysteresis of these ternary ceramics is also almost the same and low. These merits make xBMT–yPZ–zPT piezoelectric ceramics have broad application prospects in the field of commercial actuators.     

Structural and Optical Properties of Erbium and Ytterbium Codoped Germanoniobophosphate Glasses

A series of glasses with compositions of 20Na₂O–30Nb₂O₅–(5?y?z)Al₂O₃–30P₂O₅–(15?x)TiO₂–xGeO₂–yEr₂O₃–zYb₂O₃, where x = (0; 5; 10; 15), y = (0; 1), z = (0; 2) mol%, were investigated with respect to their structural, optical, and luminescence properties. The coordination of the germanium(IV) ion is normally reported as being mainly tetrahedral. However, results of this study suggest that the germanium(IV) ion may have an octahedral coordination and that TiO₂ is substituted. This proposition can be done mainly by ³¹P MAS‐NMR spectroscopy, which spectra show predominantly pyrophosphate chains in the different glasses, without changes in their polymerization after substitution. A similar coordination of germanium can also be identified by the photoluminescence behavior of the different codoped samples, which shows similar erbium(III) emission decay lifetimes (5 ms), and Judd–Ofelt intensity parameters. It was found that the upconversion emission process involved 1.5 photons. Regarding the thermal behavior, it is noted that the glasses containing higher proportions of GeO₂ exhibit higher thermal stability and are therefore more resistant to devitrification when compared to compositions containing more TiO₂.     

Patent Abstracts on Cellular Plastics

(US5019292): Granular detergent composition comprises: at least 1% detersive surfactant (I): 5–35% detergency builders (II); 1–25% naturally occurring hectorite clay ((Mg_3x Li _x )Si_4-y MeIII _y O₁₀(OH_2-z F _z )) - [(x+y) (x+y) Mn⁺]/n (III); and 1–10% additional fabric softener (IV) of formula (a) R₁R₂R₃N, (b) R₁OR₁NCOR₁₂: where MeIII is Al, Fe, or B, or y = 0; Mn⁺ is mono- or divalent metal; the clay (III) has a layer charge distribution (x+y) such that at least 50% of the layer charge is 0.23–0.31; R₁, = 6–20 C hydrocarbyl; R₂ = 1–20 C hydrocarbyl; R₃ = H or 1–20 C hydrocarbyl; R₁₀, R₁₁ = 1–22 C alk(en)yl, hydroxy alkyl, aryl, alkaryl; R₁₂ = H, 1–22 C alk(en)yl, aryl, alkaryl or OR₁₃; R₁₃ = 1–22 C alk(en)yl, aryl, alkaryl, or (c) a 1-(12–22 C alkyl) amide (1–4 C alkyl)-2-(12–22 C alkyl) imidazoline.     

Properties of Ca–(Y)–Si–Al–O–N–F Glasses: Independent and Additive Effects of Fluorine and Nitrogen

Thirty glasses of composition (in equivalent percent) 20‐xCa:xY:50Si:30Al:(100‐y‐z)O:yN:zF, with x = 0, 10; y = 0, 10, 20, and z = 0, 1, 3, 5, 7 were prepared by melting and casting. All glasses were X‐ray amorphous. Glass molar volumes (MV) decreased with nitrogen substitution for oxygen for all fluorine contents and, correspondingly, glass fractional compactness increased. Fluorine substitution of oxygen had virtually no effect on molar volume or fractional glass compactness for the three nitrogen contents tested. Young's modulus and microhardness were virtually unaffected by fluorine substitution for oxygen while nitrogen substitution for oxygen caused increases in these two properties. Glass‐transition temperature and dilatometric‐softening point values all decreased with increasing fluorine substitution levels, while increasing nitrogen substitution caused values for these thermal properties to increase. Correspondingly, the thermal expansion coefficient increased with fluorine and decreased with nitrogen substitution levels. Using property value differences between glasses containing fluorine and the corresponding glass containing 0 eq.% F enabled 24 data points to be used to determine the effect of fluorine on T_g,dil and T_DS. The trends were linear with a gradient for both properties of the order of ?22°C (eq.% F)^?1. For the nitrogen effect, 20 data points were analyzed for trend effects. As expected from earlier work, all trends had good linearity. Gradients were for T_g,dil and T_DS +2.5°C (eq.% N)^?1, which are fairly similar to previous results in oxynitride systems. All of the data collected and its analysis clearly shows that the substitution effects of fluorine for oxygen and nitrogen for oxygen are independent and additive with the fluorine substitution. The property trends of the glasses are discussed in terms of their implications for glass structure.     

Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents

The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (Pr_xZr_(1−y)Si_(1−z)O₄; y + z = x; 0.02 < x < 0.10) specimens prepared via sol–gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, Pr_xZr_(1−y)Si_(1−z)O₄ materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent Pr_xZr_(1−y)Si_(1−z)O₄ specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.     

Properties of polyamide 6,10/poly(vinyl alcohol) blends and impact on oxygen barrier performance

The oxygen transmission rate, average volume of free‐volume cavities (V_f) and fractional free volume (F_v) of polyamide 6,10 (PA610)/poly(vinyl alcohol) (PVA) (i.e. PA610_xPVA⁰⁵_y, PA610_xPVA⁰⁸_y and PA610_xPVA¹⁴_y) blend films reduced to minimum values when their PVA contents reached corresponding optimal values. Oxygen transmission rate, V_f and F_v values obtained for optimal PA610_xPVA^z_y blown films were reduced considerably with decreasing PVA degrees of polymerization. The oxygen transmission rate of the optimal bio‐based PA610₈₀PVA⁰⁵₂₀ blown film was only 2.4 cm³ (m²·day·atm)^?1, which is about the same as that of the most often used high‐barrier polymer, ethylene–vinyl alcohol copolymer. Experimental findings from dynamic mechanical analysis, differential scanning calorimetry, wide‐angle X‐ray diffraction and Fourier transform infrared spectroscopy of the PA610_xPVA^z_y blends indicate that PA610 and PVA in the blends are miscible to some extent at the molecular level when the PVA contents are less than or equal to the corresponding optimal values. The considerably enhanced oxygen barrier properties of the PA610_xPVA^z_y blend films with optimized compositions are attributed to the significantly reduced local free‐volume characteristics. © 2017 Society of Chemical Industry