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     

Properties of polyamide 612/poly(vinyl alcohol) blends and their impact on free volume and oxygen barrier properties

Oxygen transmission rates and free volume properties (i.e. average volumes of free-volume-cavities (V_f), mean number of the free volume cavities per unit volume (I₃) and fractional free volume (F_v)) values of bio-based polyamide 612 (PA612)/poly(vinyl alcohol) (PVA) (i.e. PA612_xPVA⁰³_y, PA612_xPVA⁰⁵_y, PA612_xPVA⁰⁸_y and PA612_xPVA¹⁴_y) blend films were reduced to a minimum value, when their PVA content reached corresponding optimal values of 25, 20, 15 and 10 wt%, respectively. The minimum oxygen transmission rate, V_f, I₃ and F_v value obtained for the best PA612₉₀PVA¹⁴₁₀, PA612₈₅PVA⁰⁸₁₅, PA612₈₀PVA⁰⁵₂₀ and PA612₇₅PVA⁰³₂₅ bio-based blown films reduced considerably with decreasing PVA degrees of polymerization. As evidenced by the results of dynamical mechanical analysis, differential scanning calorimetry, wide angle X-ray diffraction and Fourier transform infrared spectroscopic experiments, PA612 and PVA are miscible to some extent at the molecular level when their PVA contents are ≤ the corresponding optimal values. The significantly improved oxygen barrier and free volume properties for the PA612_xPVA^z_y blend films with optimized compositions is at least in part to the enhanced intermolecular interactions between PA612 carbonyl groups and PVA hydroxyl groups.     

The effect of poly(vinyl alcohol) hydrolysis on the properties of its blends with nylon 6

An investigation of the properties of the blends of nylon 6 (PA6) and poly(vinyl alcohol) (PVA) with varying degrees of hydrolysis was conducted. A near disappearance of the characteristics of the α‐form PVA crystals, crystallization exotherms, and hydrogen‐bonded hydroxyl groups and the tensile properties originally associated with the PVA molecules of PA6_xPVA PA6_xPVA, and PA6_xPVA specimens was observed as the PVA contents of the specimens became equal to or less than their corresponding ‘‘critical’’ values at 16.7 wt%, 33.3 wt%, and 50 wt%, respectively. These results support the idea that PVA molecules are miscible with PA6 molecules to some extent at the molecular level as the PVA contents of the blends become equal to or less than their corresponding critical PVA contents. In this article, we have proposed the possible reasons accounting for these properties of the PA6_xPVA_y series specimens with a varying degree of hydrolysis. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Characteristics and sensing behavior of electrochemically codeposited polypyrrole–poly(vinyl alcohol) thin film exposed to ethanol vapors

Polypyrrole–poly(vinyl alcohol) (PPy–PVA) composite films were prepared electrochemically by means of codeposition at a constant potential. Their sensing behaviors to various ethanol-vapor concentrations were investigated. Increasing the molar fraction of PVA up to PPy_0.964PVA_0.036 showed an increase of the sensitivity of the composite sensors. However, the sensitivity decreased if further PVA was incorporated. The ethanol-sensing behaviors were also largely dependent upon the electropolymerization charge, ranging from 50 to 200 mC in this investigation. Higher sensitivity was measured from the composite film prepared with a lower electrical charge. For example, a sensitivity of 7.70 mΩ mg⁻¹ L, about 3.3 times the sensitivity of the pristine PPy sensor, was measured by the PPy_0.964PVA_0.036 composite film prepared at 50 mC. However, incorporating PVA into the conducting polymer was at the sacrifice of the response speed as well as the stability of the composite as it was under continuous exposure to ethanol vapor. An adsorption model based on the Langmuir isotherm was used to interpret the sensing behaviors and the equation derived from this model correlated well with the measured sensitivities. The sensing parameters including the adsorption equilibrium constant, K_m, and the resistance change caused by a pseudomonolayer, [m(r₁ − r₂)]/n, were determined and found to decrease with increasing polymerization charge. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2079–2087, 1999     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

Effects of Plasticizing on Mechanical and Viscous Characteristics of Poly(vinyl alcohol): A Comparative Study between Glycerol and Diethanolamine

Although plasticizing materials by modification with small-molecular chemicals has been extensively utilized in the industrial community, processing poly(vinyl alcohol) (PVA) at high concentrations (C_PVA) or with a high degree of polymerization (DP) remains challenging. Optimization the plasticizing conditions is one means of addressing this issue. In this study, two types of frequently used plasticizers, glycerol (GLY) and diethanolamine (DEA), are chosen to plasticize PVA resin with a DP of 2400. Both PVA/plasticizer films possess excellent optical transmittance and mechanical ductility, whereas the films blended with DEA exhibit higher strength than the PVA/GLY films. The viscosity variation in the temperature (T_op)–C_PVA space is monitored by real-time viscous flow testing, demonstrating that DEA is more effective for reducing the viscosity of PVA, which should improve the processability, facilitating film-forming from concentrated solutions. Furthermore, density functional theory calculations and molecular dynamics simulations illustrate that the PVA/DEA system has a lower binding energy, longer hydrogen bond length, and higher isotropic diffusion coefficient, indicating a stable hydrogen bond network and homogenous dispersion of the plasticizer, leading to good solution fluidity and mechanical performance. This study is significant for guiding the design and manufacture of optically transparent, high-performance PVA films as polarizer precursor.     

A transdermal diltiazem hydrochloride delivery device using multi-walled carbon nanotube/poly(vinyl alcohol) composites

Membranes with high strength and elasticity are of great demand in patch therapy. Similar membranes have been developed by combining carboxy-functionalized multiwalled carbon nanotube (c-MWCNT) with different poly(vinyl alcohol) (PVA) as potential diltiazem delivery device through aqueous mixing. High molecular weight PVA (PVA_H) produced stronger interaction with c-MWCNT than low molecular weight PVA (PVA_L) preferably at low concentration. Positive changes in favor of PVA_H in infrared and solid state ¹³C nuclear magnetic resonance spectroscopy, wide angle X-ray scattering, thermal stability, morphology and dry and wet mechanical properties clearly demonstrate that. Fibrillar c-MWCNT array at 1 wt.% in PVA_H (PVA_H/1) has drastically improved PVA crystalline cell dimension, tensile strength (201%) and elongation (196%) than neat PVA_H whereas the similar improvement is much less (100% and 185%) in PVA_L (PVA_L/1) due to globular morphology. Instead, c-MWCNT performed better at 0.5 wt.% in PVA_L (PVA_L/0.5). The kinetic data reflects better encapsulation and slower release by PVA_H (5.87%) than PVA_L (10.17%) due to greater interfacial interaction.     

Air-based sputtering deposition of titanium oxynitride-based single,gradient, and multi-layer thin films for photoelectrochemical applications

Titanium oxynitride (TiN_xO_y) thin films exhibiting tunable physical and chemical properties can be used in many fields. Air-based sputtering deposition of the films with diverse O/N ratios was employed to produce gradient and multilayer films. By solely altering the air/Ar flow ratio, obtained TiN_xO_y films could change from a crystalline to a mainly amorphous feature. Moreover, the carrier concentration, Hall mobility, and hence resistivity of the films could be modified to a large range. The optical bandgaps of the films could also be tailored to a wide extent. Based on these results, the gradient TiN_xO_y layer and TiN_xO_y/TiN(O) multilayer were also deposited on TiN(O)-coated glass substrates for the assessment of photoelectrochemical performance. Compared with the TiN_xO_y/TiN(O) bilayer with the best photoelectrochemical performance, the photoelectrochemical currents of gradient TiN_xO_y films could be improved from 99 ± 2 μA⋅cm⁻² to 164 ± 2 μA⋅cm⁻² by taking advantage of bandgap engineering. Additionally, the photoelectrochemical currents of TiN_xO_y/TiN(O) multilayer were further improved to 175 ± 6 μA⋅cm⁻². This is mainly due to conductive nano TiN(O) layers providing multiple high-transport paths while allowing light transmission. The enhancement mechanisms of the gradient and multilayer films have also been elaborated.     

Direct electrochemical detection of pyruvic acid by cobalt oxyhydroxide modified indium tin oxide electrodes

An enzyme-free electrode was fabricated by anodic electrodeposition of cobalt oxyhydroxide film on an ITO electrode (CoO_x(OH)_y/ITO) for direct electrochemical detection of pyruvic acid (PA) in solution. Scanning electron microscopy (SEM) and atom force microscopy (AFM) were employed to characterize the morphology of CoO_x(OH)_y film. Cyclic voltammetry (CV) was used to investigate the electrochemical properties of PA on CoO_x(OH)_y/ITO in order to select the optimal potential for the chronoamperometric detection of PA. It was found that the CoO_x(OH)_y/ITO electrode served as an excellent PA sensor with a linear detection range of 1.00 μM to 1.91 mM, a detection limit of 0.55 μM, and a high sensitivity of 417.1 μA mM⁻¹ cm⁻². Moreover, the response time of CoO_x(OH)_y/ITO to PA is less than 10 s, which is the shortest for PA detection reported in literature using electrochemical method. These properties and the high stability of CoO_x(OH)_y/ITO made it a good candidate for developing electrochemical enzyme-free PA sensing device.     

Laser ablation of Ga-Sb-Te thin films monitored with quadrupole ion trap time-of-flight mass spectrometry

Laser ablation of Ga-Sb-Te chalcogenide thin films prepared by radiofrequency magnetron co-sputtering was monitored with quadrupole ion trap time-of-flight mass spectrometry (QIT-TOF-MS). The mass spectra of 11 thin films of various compositions (Ga: 0–53.1, Sb: 0–52.0, and Te: 0–100.0 at. %) were recorded. Several series of unary (Ga_x, Sb_y, and Te_z) binary (Ga_xSb_y, Ga_xTe_z, and Sb_yTe_z), and ternary Ga_xSb_yTe_z clusters were identified in both positive and negative ion modes. Stoichiometry of observed clusters was determined. Up to 18 binary clusters (positively and negatively charged) were detected for thin film with low Sb content of 6.5 at. %. The highest number (4) of ternary clusters was observed for thin film with high Te content of 66.7 at. %. The number of generated clusters and their peaks intensity varied according to the chemical composition of thin films. Altogether, 41 clusters were detected. The laser ablation monitoring shows laser-induced fragmentation of thin film structure. The relation of clusters stoichiometries to the chemical composition of thin films is discussed. The fragmentation can be diminished by covering a surface of thin films with paraffin's, glycerol, or trehalose sugar thin layers. The stoichiometry of generated clusters shows partial structural characterization of thin films.     

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.     

Mechanical properties of films of poly(vinyl alcohol) derived from vinyl trifluoroacetate

In order to study the influence of the stereoreguralities of polymer chains on the mechanical properties of films of poly(vinyl alcohol) (PVA)_(VTFA) derived from vinyl trifluoroacetate, the strength of the film was measured. In the case of undrawn PVA_(VTFA) films, Young's modulus and strength at break were the smallest at the annealing temperature of about 100°C. It is considered to be due to the melt of small microcrystals and the increase in mobility of chains in amorphous parts. Young's moduli of undrawn PVA_(VTFA) films were in the range of 1.50–3.75 GPs and the values were higher than that (0.17–0.36 GPa) of undrawn film of commercial PVA with the low concentration of syndiotacticity and the high concentration of head-to-head bounds. In the case of drawn, annealed PVA_(VTFA) films, the maximum Young's modulus was about 20 GPa.     

New isopolyoxovanadate ions identified by electrospray mass spectrometry

Ammonium metavanadate in aqueous solution at pH 4.5 displays in electrospray mass spectrometry experiments the presence of the two series of anions [H_xV_yO_z]⁻ (x=0, 1; y=1–9; z=3–23) and [H_xV_yO_z]²⁻ (x=0, 1; y=3–17; z=9–44) as well as [H₂VO₄]⁻, [V₁₀O₂₈]⁶⁻ and [H₅V₁₀O₂₈]⁻ ions. Further, the cation series [H_m+1(VO₃)_m]⁺ (m=1–6), [H_m−1V_mO_3m−1]⁺ (m=4–10) and [H_m−3V_mO_3m−2]⁺ (m=6–11) are observed. The series of protonated and unprotonated anions differ by {V₂O₅} units, the formal building block in these clusters. A range of polyoxovanadates not previously reported have been observed.     

Comparison of dissolution and mutual diffusion coefficients during dissolution of poly(methyl methacrylate) films

Steady state fluorescence measurements have been used for studying the dissolution of polymer films. These films are formed by free radical polymerization of methyl methacrylate (MMA) in which pyrene ( P_y ) was introduced as a fluorescence probe. Dissolution of poly(methyl methacrylate) (PMMA) films in chloroform–heptane mixtures were monitored in real-time by the P_y fluorescence intensity change. Dissolution coefficients D_d of P_y molecules were measured during dissolution of PMMA films, and found to be about 10⁻⁶ cm² s⁻¹. After dissolution, fluorescence quenching measurements were performed and the Stern–Volmer equation was employed to measure the mutual diffusion coefficients of heptane (D_h) and P_y (D_Py) molecules; these were found to be about 10⁻⁵ cm² s⁻¹. © 1999 Society of Chemical Industry     

Dialdehyde polyethylene glycol cross-linked poly(vinyl alcohol) membranes with enhanced CO2/N2 separation performance

The development of carbon dioxide (CO₂) separation technology is crucial for mitigating global climate change and promoting sustainable development. In this study, we successfully synthesized an array of cross-linked poly(vinyl alcohol) (PVA) membranes, xALD-PEG-ALD-c-PVA, with enhanced CO₂/N₂ separation performance by employing dialdehyde polyethylene glycol (ALD-PEG-ALD) as a cross-linker. The formation of the cross-linked network structure not only inhibits the crystallization of PVA but also disrupts hydrogen bonding and thus increases fractional free volume of PVA chains. Under the synergistic effect of these multiple factors, the cross-linked PVA membranes exhibit a significantly improved CO₂ permeability. Moreover, they maintain high CO₂/N₂ selectivity, attributing to the CO₂-philic characteristic of ethylene oxide groups in the cross-linked structure. At the ALD-PEG-ALD content of 1.6 mmol g⁻¹, the xALD-PEG-ALD-c-PVA membrane demonstrates a CO₂ permeability of 41.4 barrer and a CO₂/N₂ selectivity of 57.4 at 2 bar and 25°C. Furthermore, compared with the pristine PVA membrane, xALD-PEG-ALD-c-PVA membranes manifest superior mechanical properties and outstanding separation performance for a CO₂/N₂ (15/85, vol%) gas mixture. The excellent combination of permeability and selectivity makes xALD-PEG-ALD-c-PVA membranes highly promising for various CO₂ separation applications.     

Preparation of silicon carbide–silicon nitride fibers by the controlled pyrolysis of polycarbosilazane precursors

Experiments to produce polycarbosilazane resin and high-strength silicon carbide–silicon nitride (Si_xN_yC_z) fibers as well as resin/fiber characteristics are reported. Polycarbosilazane resin was drawn into fibers from the melt and subsequently treated and pyrolyzed into Si_xN_yC_z fibers. These materials are characterized by high tensile modulus (29 × 10⁶ psi for 0.4-mil diameter) and high electrical resistivity (6.9 × 10⁸ Ω·cm for 0.6-mil diameter).     

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.     

A Model of Mechanotransduction in Polyvinyl Alcohol-Based Composite Hydrogels for Regulating Musculoskeletal Differentiation

In regenerative medicine, extracellular matrix (ECM)-inspired materials are currently being explored to imitate mechanotransduction pathways and control cell fate. In musculoskeletal tissue regeneration, enhancing mechano-biological signals require biomaterials that are both biocompatible and viscoelastic and can retain water content. Herein, based on these requirements, various polyvinyl alcohol (PVA)-based composite hydrogels, reinforced by polyhydroxy butyrate (PHB) nanofibers, are proposed to differentiate equine adipose-derived stem cells for musculoskeletal regeneration. To study the role of fiber embedding in improving scaffold properties, different nanofiber assemblies, including chopped short ones with random orientation (PVA_S), single-layer (PVA_L1), and double-layer membranes (PVA_L2) are positioned into the PVA matrix. PHB reinforcements negatively affect swelling and positively enhanced phase transition temperatures and crystallinity of PVA hydrogel. According to mechanical analysis results, compositing with PHB nanofibrous layers strengthen the PVA matrix due to some restrictions on PVA chain mobility. Gene expression investigations also reveal that higher matrix stiffness after layering with two PHB membranes (PVA_L2) promotes osteogenesis, while the random addition of short-chapped fibers (PVA_S) facilitate tenogenic differentiation. As a consequence of the findings, fiber placement is crucial to the mechanical properties of composite hydrogels that ultimately control musculoskeletal differentiation signals through mechanosensing pathways.     

Optimization of electrical conductivity in the Na2O-P2O5-AlF3-SO3 glass system

We report on the individual roles of charge carrier density and network modification in sodium ion conducting glasses from the Na₂O-P₂O₅-SO₃-AlF₃ (NAPFS) system. For this, a broad range of glass compositions was considered across the series of 44Na₂O/(56 – x − y)P₂O₅/xAlF₃/ySO₃, 47Na₂O/(53 − x − y)P₂O₅/xAlF₃/ySO₃, and 50Na₂O/(50 − x − y)P₂O₅/xAlF₃/ySO₃, with x = 8, 12, 16, 20 and y = 0, 5, 7, 10, 12. Impedance spectroscopy was conducted on these glasses at frequencies from 10⁻² to 10⁶ Hz and over temperatures from 50 to 250°C, and complemented by structural analyses using Raman spectroscopy and nuclear magnetic resonance data. While the trends in dc conductivity and activation energy follow that of Na₂O content (increasing from 44 to 50 mol%), substantial enhancement of conductivity (by about two orders of magnitude) and correspondingly lower activation energy were also found for constant Na₂O concentration when adjusting SO₃ or AlF₃ within specific limits of glass structure.     

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.