Thermodynamics of micellization of poly-styrene-block-poly(ethylene/propylene) copolymers in decane

Light scattering was used to establish the dependence of the critical micelle temperature, CMT, on concentration for solutions of three polystyrene-block-poly(ethylene/propylene) copolymers in decane. Electron microscopy studies of particles isolated from the solutions showed that the micelles had narrow size distributions and micellization could be treated thermodynamically as a closed association. The light scattering results were used to calculate the standard Gibbs energies of micellization, ΔG^φ, and the standard enthalpy, ΔH^φ, and entropy contributions, —TΔS^φ. The values of ΔH^φ were large and negative, and markedly dependent on the molecular weight of the polystyrene block. The values of ΔG^φ for the three samples were on the other hand very similar to each other. The standard entropy contributions were unfavourable to micelle formation.     

Effect of end-group modification,hydrophilic/hydrophobic block ratio and temperature on the surface,associative and thermodynamic behaviour of poly(ethylene oxide)-b-poly(butylene oxide) diblock copolymers in aqueous media

This study describes the surface, micellar, associative and thermodynamic properties of four diblock oxyethylene (E)/oxybutylene (B) copolymers with different hydrophilic block ends and various hydrophilic/hydrophobic ratios in aqueous media. The copolymers were denoted DE₄₀B₁₈, TE₄₀B₁₈, E₅₆B₁₉ and E₅₆B₇. The aqueous polymer solutions at various concentrations and temperatures were investigated by surface tensiometry and dynamic and static laser light scattering. Surface tension measurements were employed to detect the critical micelle concentration (CMC) as well as to calculate the surface-active and thermodynamic parameters of adsorption at the air/water interface. CMC values were also used to calculate the enthalpy of micellization (?H ⁰ _mic), free energy of micellization (?G ⁰ _mic) and entropy of micellization (?S ⁰ _mic). Similarly, various thermodynamic parameters for adsorption at the air/water interface were also deduced. Dynamic light scattering (DLS) was used to obtain the hydrodynamic radii (r _h) and volumes (υ _h) of the micelle at different temperatures, and hence the hydrodynamic expansion parameter (δ _h) was also estimated. Likewise, static light-scattering measurements enabled us to determine various parameters of the copolymer micelles, such as the weight-average molar mass (M _w), association number (N _w), thermodynamic radius (r _t), thermodynamic volume (υ _t), anhydrous volume (υ _a) and the thermodynamic expansion parameter (δ_t). Various thermodynamic and micellar parameters obtained from light scattering show that the micelles formed are spherical in shape and have rather soft interaction potentials at low temperature but become harder at higher temperature. Based on the different experimental results obtained, it can be said that various surface, micellar and thermodynamic parameters are dependent not only on the temperature and solution conditions but also on the hydrophobic/hydrophilic ratio and the end-group composition of the polymer. Modification of the hydrophilic end group of the polymer prominently affects various micellar properties. This effect can be assigned to the difference in polarity and the intermicellar charge effect.     

Phosphoric acid doped poly(2,5‐benzimidazole)‐based proton exchange membrane for high temperature fuel cell application

Undoped and doped poly(2,5‐benzimidazole) (ABPBI) membrane was prepared by solvent casting method using methane sulfonic acid as a solvent and phosphoric acid (H₃PO₄) as a doping agent. The concentration of H₃PO₄ was varied from 0 to 60 vol% to enhance the proton conductivity of the ABPBI membrane at higher temperature. Wide angle X‐ray diffraction analysis showed a decrease in crystallinity in ABPBI membrane with increase in H₃PO₄ doping concentration. The molecular signature and the presence of H₃PO₄ was observed in 1000–1500 cm^?1 in the Fourier transform infrared spectra, which was also supported by a corresponding weight loss at 180°C–200°C in the thermogravimetric analysis. Undoped ABPBI membrane registered the Young's modulus (E) and hardness (H) values of 2.46 and 0.92 GPa, respectively, and the corresponding E and H values for 1.65 doping level of 60 vol% H₃PO₄ doped ABPBI membrane were 0.14 and 0.067 GPa, respectively. The 60 vol% H₃PO₄ doped ABPBI membrane with doping level of 1.65 showed highest proton conductivity value of 2.2 × 10^?2 S/cm. The impedance spectroscopic analysis and the equivalent circuit model were discussed to understand the nature of proton conduction in H₃PO₄ doped ABPBI membrane. POLYM. ENG. SCI., 56:1366–1374, 2016. © 2016 Society of Plastics Engineers     

磺化聚苯并咪唑/二氧化硅杂化质子交换膜的制备及性能

为改善磺化聚苯并咪唑的综合性能,用异氰酸丙基三乙氧基硅烷作为偶联剂,正硅酸乙酯作为前驱体,在膜内生成有机-无机杂化交联网络,制备了燃料电池用高温质子交换膜。利用傅里叶转变红外光谱（FTIR）表征了聚合物膜的化学结构。用扫描电镜(SEM)观察了聚合物膜的断面形貌。利用交流阻抗（EIS）测定了聚合物膜在磷酸掺杂后的质子传导率。研究结果表明,硅烷偶联剂的加入使得界面相容性良好。由于存在有机-无机交联结构,在膜的溶胀增加不大的前提下,磷酸掺杂量得到了增加,相应地增加了聚合物膜的质子传导率。     

Corrosion Behaviour of Ti–4Al–4V Alloy in Nitric, Phosphoric and Sulfuric acid Solutions at Room Temperature

Electron beam melting of Ti-6-4 scrap has been carried out. Aluminium losses were verified for all the runs and commercial-size ingots of Ti-4-4 alloy were obtained. Tensile tests and hardness measurements have shown that the Ti-4-4 alloy has mechanical strength close to the Ti-6-4 alloy as well as higher ductility. The corrosion behaviour of the Ti-4-4 alloy was investigated in HNO₃, H₃PO₄ and H₂SO₄ solutions at room temperature. Ti-4-4 alloy is passive in all HNO₃ solutions and in 20 wt% H₃PO₄ and presents an active behaviour in 40–80 wt% H₃PO₄ and in all H₂SO₄ solutions. Ti-4-4 alloy is highly corrosion resistant in HNO₃ and 20 wt% H₃PO₄ and has a moderate resistance in 40 wt% H₃PO₄. Ti-4-4 alloy can be regarded as a potential candidate to replace CP–Ti in these media. In more concentrated H₃PO₄ solutions, and in H₂SO₄, very high corrosion rates were observed.     

Synthesis and thermal responsive properties of P(LA-b-EO-b-PO-b-EO-b-LA) block copolymers with short hydrophobic poly(lactic acid) (PLA) segments

Poly(lactic acid) (PLA) was successfully grafted to both ends of Pluronic F87 block copolymer (PEO-PPO-PEO) to obtain amphiphilic P(LA-b-EO-b-PO-b-EO-b-LA) block copolymers (PLA-F87-PLA) with short PLA blocks. The block composition and structure of PLA-F87-PLA block copolymers were studied by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetric (DSC) and wide angle X-ray diffraction (WXRD) techniques. The aggregation behavior of PLA-F87-PLA block copolymers in aqueous solutions was studied using the laser light scattering (LLS) technique. Various types of particles consisting of small micelles, medium and large aggregates were observed due to the complex structure of these copolymers. Importantly, PLA-F87-PLA block copolymers retain the thermal responsive behavior found in Pluronic systems. The critical micellization temperatures (CMTs) of PLA-F87-PLA were lower than that of F87 because of increased hydrophobicity introduced by the PLA blocks. A reversible sol-gel transition was observed for the hydrogels formed from PLA₆-F87-PLA₆ and PLA₉-F87-PLA₉ block copolymers. Preliminary results from the drug release study using a hydrophilic model drug procain hydrochloride (PrHy) were promising. Constant initial release rate was observed.     

Influence of end-group modification on interaction of amphiphilic poly(oxyethylene)-<Emphasis Type="Italic">b</Emphasis>-poly(oxybutylene) block copolymers with ionic surfactants

Amphiphilic poly(oxyethylene)-b-poly(oxybutylene) block copolymers having hydrophilic block end-capped with neutral dimethylamino (DE₇₉B₃₄) and cationic trimethyl ammonium (TE₇₉B₃₄) groups, respectively were investigated for their interactions with ionic surfactants, sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) using tensiometry, conductometry and dynamic light scattering. The self-assembly of DE₇₉B₃₄ and TE₇₉B₃₄ occur at 0.7 g/dm³ and 0.8 g/dm³, respectively. TE₇₉B₃₄ binds favorably with oppositely charged SDS, causing a substantial change in surface tension compared to other surfactant-polymer systems. In mixed polymer-surfactant systems, the micellization was promoted in the presence of SDS, but it was suppressed with CTAB. Such behavior is expected for cationic block copolymers, since they can engage into ion-pair formation with anionic SDS. For neutral polymers, the behavior is reflective of surfactants’ head group hydrophobicity. The head groups of CTAB are more hydrophobic and their existence in the proximity of hydrophobic segments of polymers induces shape transition to non-spherical morphologies. Gibb’s free energy of adsorption at air – water interface is negative for SDS, CTAB and surfactant-block copolymer systems, indicating that the process is highly spontaneous. The increase in entropy of TE₇₉B₃₄ during micelle formation with temperature is due to disturbance of hydrophobic structure of water molecules, thus hydrophobic parts are removed from bulk solution to the interface and also in the interior of micelle the freedom of hydrophobic part is increased. The dynamic laser light scattering results revealed that due to presence of block copolymers pre-micellar aggregates were favored.     

Preparation and Characterisation of Proton Exchange Membranes Based on Crosslinked Polybenzimidazole and Phosphoric Acid

Crosslinked polybenzimidazole (PBI) was synthesised via free radical polymerisation between N‐vinylimidazole and vinylbenzyl substituted PBI. The degree of crosslinking increases with increasing content of the crosslinker. The phosphoric acid doping behaviour, mechanical properties, proton conductivity and acid migration stability of crosslinked PBI and linear PBI are discussed. The results show that the acid doping ability decreases with increasing degree of crosslinking of PBI. The introduction of N‐vinylimidazole in PBI is beneficial to its oxidation stability. The mechanical stability of crosslinked PBI/H₃PO₄ membrane is better than that of linear PBI/H₃PO₄ membrane. The proton conductivity of the acid doped membranes can reach ∼10^–4 S cm^–1 for crosslinked PBI/H₃PO₄ composite membranes at 150 °C. The temperature dependence of proton conductivity of the acid doped membranes can be modelled by an Arrhenius relation. The proton conductivity of crosslinked PBI/H₃PO₄ composite membranes is a little lower than that of linear PBI/H₃PO₄ membranes with the same acid content. However, the migration stability of H₃PO₄ in crosslinked PBI/H₃PO₄ membranes is improved compared with that of linear PBI/H₃PO₄ membranes.     

Studies on the block copolymerization of D,L-lactide and poly(ethyle glycol) with aluminium complex catalyst

A series of block copolymers from D,L-lactide and poly(ethylene glycol) (PEG) with different molecular weight were synthesized by using Al(i-Bu)₃? H₃PO₄? H₂O as the initiator and identified by ¹H-NMR, GPC, and DSC. The elongation at break of the material increased when PEG was introduced, but the strength of the material decreased. The copolymers degrade more smoothly in vitro than did the PLA homopolymer. © 1995 John Wiley & Sons, Inc.     

Synthesis of block copolymers based on oxyethylene chains and their use as polymer electrolytes

High-molecular-weight copolymers were prepared consisting predominantly of oxyethylene and oxymethylene-oligo(oxyethylene) blocks with a small 1-phenylethylene block. Ionic conductivities of mixtures of the copolymers with CF₃SO₃Li were measured.     

Poly[N-(2-hydroxypropyl)methacrylamide-block-n-butyl acrylate] micelles in water/DMF mixed solvents

Three diblock copolymers of poly[N-(2-hydroxypropyl)methacrylamide] (poly(HPMA)) and poly(n-butyl acrylate) (poly(BA)) with varying lengths of blocks were prepared by atom transfer radical polymerization. All copolymers were found to be soluble in dimethylformamide (DMF) and poorly soluble or insoluble in water. In water and mixed DMF/H₂O solvents, the copolymers were dispersed in micellar form by controlled addition of water to DMF solutions of copolymers under continuous intensive stirring. The micellar solutions in water were prepared by dialysis of solutions in DMF/H₂O (95 vol% of H₂O) against water. Solution properties of diblock copolymers of poly(HPMA) and poly(BA) were studied using static and dynamic laser light scattering to characterize the behavior of the copolymers at the supramolecular level. The effects of preparation mode, organic solvent (DMF) and copolymer chemical composition on the formation of micelles were studied. While a slower mixing procedure was optimal for copolymers with short poly(HPMA) blocks, a faster mixing was more suitable for copolymers having longer poly(HPMA) blocks. Finally, the dimensions of micelles in water were evaluated. The most compact micelles were prepared from copolymers having short hydrophilic poly(HPMA) blocks. On the other hand, the copolymer with the longest poly(HPMA) block formed micelles with the smallest size and the lowest density.     

Study of the oxygen reduction reaction (ORR) at Pt interfaced with phosphoric acid doped polybenzimidazole at elevated temperature and low relative humidity

The oxygen reduction reaction on platinum interfaced with phosphoric acid doped PBI at elevated temperature and low relative humidities has been investigated by using a micro band electrode technique. Both the kinetic and the mass transport parameters in the Pt/PBI-H₃PO₄ system are comparable to those of the Pt/H₃PO₄ system under similar conditions. The study suggests that it is the amorphous H₃PO₄ phase that functions as the electrolyte. The oxygen reduction reaction is first order with respect to both proton concentration and oxygen saturation concentration in the electrolyte, which indicates that the proton transfer is the rate-determining step in oxygen reduction. The H₃PO₄ doping level and the water content of the electrolyte affect the ORR exchange current density, oxygen diffusion, and the oxygen solubility in PBI-H₃PO₄ membranes. The dissolved O₂ molecules permeate mainly through the amorphous H₃PO₄. However, the oxygen solubility in PBI-H₃PO₄ is higher than its solubility in H₃PO₄, which is explained by the presence of the crystalline PBI region formed during electrolyte preparation.     

Crystallization and coalescence of block copolymer micelles in semicrystalline block copolymer/amorphous homopolymer blends

Crystallization of two oxyethylene/oxybutylene block copolymers (E₇₆B₃₈ and E₁₅₅B₇₆) from micelles in block copolymer/amorphous homopolymer blends was studied by differential scanning calorimetry (DSC) and time-resolved small angle X-ray scattering (SAXS). Unlike the simultaneous crystallization and formation of superstructure in crystallization from an ordered structure, crystallization of block copolymer from micelles can be divided into two steps. The core of the micelles firstly crystallizes individually, with first-order crystallization kinetics and homogeneous nucleation mechanism. The SAXS revealed that crystallization-induced deformation occurs for the micelles, which strongly depends on microstructure of the block copolymers. For the shorter block copolymer E₇₆B₃₈, larger deformation induced by crystallization was observed, leading to coalescence of the micelles after crystallization, while for the longer block copolymer E₁₅₅B₇₆ the micelles show little deformation and the morphology of micelle is retained after crystallization.     

Surface activity and micellar behavior of dimethylamino‐ and trimethylammonium‐ tipped oxyethylene–oxybutylene diblock copolymers in aqueous media

Surface activity and micellar behavior in aqueous media in the temperature range 20–50°C of the two block copolymers, Me₂N(CH₂)₂OE₃₉B₁₈, (DE₄₀B₁₈) and I^?Me₃N⁺(CH₂)₂OE₃₉B₁₈, (TE₄₀B₁₈) in the premicellar and postmicellar regions have been studied by surface tensiometry, viscometry, and densitometry. Where E represents an oxyethylene unit while B an oxybutylene unit. Various fundamental parameters such as, surface excess concentrations (Γ_m), area per molecule (a) at air/water interface and standard Gibbs free energy for adsorption, ΔG have been investigated for the premicellar region at several temperatures. The thermodynamic parameters of micellization such as, critical micelle concentrations, CMC, enthalpy of micellization, ΔH, standard free energy of micellization ΔG, and entropy of micellization ΔS have also been calculated from surface tension measurements. Dilute solution viscosities have been used to estimate the intrinsic viscosities, solute‐solvent interaction parameter and hydration of micelle. Partial specific volume and density of the micelle were obtained from the density measurements at various temperatures. The effect of modifying the end group of the hydrophilic block was investigated by comparing the behavior of trimethylammonium‐ and dimethylamino‐tipped copolymers, designated TE₄₀B₁₈, and DE₄₀B₁₈, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrochemical behaviour of a vanadium anode in phosphoric acid and phosphate solutions

Anodic polarisation of a vanadium electrode has been studied in H₃PO₄ solutions and some phosphate solutions: LiH₂PO₄, NaH₂PO₄, KH₂PO₄ and NH₄H₂PO₄. The anodic behaviour of a vanadium electrode showed similarities in weak concentrated H₃PO₄, in LiH₂PO₄ and NaH₂PO₄ solutions: the polarisation curve exhibited a current peak followed by current oscillations and then a current plateau. Concentrated H₃PO₄, 1 M KH₂PO₄ and NH₄H₂PO₄ solutions involved vanadium passivation with a very slight current density plateau. Yellow compound identified to VOPO₄·2H₂O was obtained after controlled potential oxidation of vanadium in 5-10 M H₃PO₄. Green products were obtained in 1 M phosphate solutions and in 1-3 M H₃PO₄ on vanadium anode after controlled potential electrolysis. All these vanadophosphate compounds contained the monovalent cation which was present in the solution.     

Alkanol-Induced Micelles of a Very Hydrophilic EO–PO–EO Block Copolymer: Characterization by Spectral and Scattering Methods

The aqueous solution behavior of a PEO–PPO–PEO block copolymer (EO₁₀₃PO₃₉EO₁₀₃), was investigated in the presence of aliphatic alkanols (C₂, C₄, C₆ and C₈). The non-associated polymer chains remain extremely hydrated in water, but aggregation in the form of spherical micelles was evidenced, triggered by the interaction of polymer chains with hydrophobic alkanol. We assume that the hydrophobic interaction between the PPO block of the copolymer and alkanol promotes micellization, which increases further with the introduction of higher chain length species. The critical micellization temperature (CMT), as measured by UV–visible spectroscopy, indicates an interaction of polymer chains with the alkanol bearing a higher chain length, which triggers aggregation. The micelles were characterized by small angle neutron scattering to elucidate the size and related micellar parameters. The gradual increase in the alkanol content increases the aggregation number, though the micelles were spherical in shape. We conclude that ethanol, due to its preferential solubility in the aqueous phase, does not affect the aggregation. The alkanols with chain lengths of C₄–C₈ chain, interact with the PPO block through hydrophobic interaction and shifts the CMTs to lower values. The combined effect of inorganic salt (NaCl) and alkanols show enhanced micellar properties.     

Thermoreversible micellization and gelation of a blend of pluronic polymers

Aqueous solutions of a blend consisting of a PEO-PPO-PEO triblock copolymer, Pluronic F127 (EO₁₀₀-PO₆₅-EO₁₀₀) and a PPO-PEO-PPO triblock copolymer, Pluronic-R 25R4 (PO₁₉-EO₃₃-PO₁₉) were studied. Thermoreversible micellization and gelation properties of the blend were examined as a function of temperature and molar ratio of 25R4 to F127 by means of micro DSC and rheology. The completely thermoreversible behaviors of micellization and gelation were observed for all the blend solutions with two F127 concentrations (10 and 15 wt%) and various 25R4/F127 molar ratios (0-4) even though the pure 25R4 solution itself was not thermoreversible. At a given concentration of F127, three effects of 25R4 on F127 were found as follows. (a) The micellization temperature of F127 shifts to a lower temperature with increasing 25R4 content, implying a “salt-out like” effect of 25R4. (b) Beyond the primary peak for micellization a secondary peak appears due to the effect of 25R4. (c) At the molar ratio of 25R4/F127 = 3:1, the gelation of the 15 wt% F127 solution occurs twice at low and high temperatures, respectively. When the ratio > 3:1, the gelation occurs only at high temperatures. The possible mechanisms involved in these unique behaviors of micellization and gelation have been proposed and discussed. The effect of 25R4 on F127 was compared with another Pluronic polymer F108 (EO₁₃₃-PO₅₀-EO₁₃₃).     

Raman characterization and photoluminescence properties of La1-xTbxPO4·nH2O and La1-xTbxPO4 phosphor nanorods prepared by microwave-assisted hydrothermal synthesis

The effect of the Tb³⁺–doping content (in the range 0–100 mol%) on the structure (using Raman spectroscopy) and photoluminescence (PL) properties of both rhabdophane-type La_1-xTb_xPO₄·nH₂O and monazite-type La_1-xTb_xPO₄ single-crystal nanorods was investigated. La_1-xTb_xPO₄·nH₂O was directly obtained by microwave-assisted hydrothermal synthesis and La_1-xTb_xPO₄ by calcination of La_1-xTb_xPO₄·nH₂O at 700 °C in air for 2 h. It was found that the characteristic Raman bands shift to higher wavenumbers and become broader with increasing Tb³⁺ concentration, which is attributed to attendant unit-cell volume reduction. The PL due to the Tb³⁺ f-f transitions has been studied with continuous and pulsed excitations. The PL intensity increases with doping and is maximum for La_0.80Tb_0.20PO₄·nH₂O and La_0.85Tb_0.15PO₄, i.e., for rhabdophane and monazite-type structures, respectively. A quenching effect is detected for concentrations below x=0.05, but constant efficiency is obtained at higher doping. The calcination increases the efficiency by a factor around 2 due to the combined effects of water molecules and defect elimination. The PL decay curves reveal a long lifetime attributable to single Tb³⁺ ions which is almost independent of doping for monazite nanorods (5–4.5 ms), and a shorter one around 0.2 ms most likely due to Tb³⁺ dimmers.     

Micellization and phase transition behavior of thermosensitive poly(N-isopropylacrylamide)-poly(?-caprolactone)-poly(N-isopropylacrylamide) triblock copolymers

Thermosensitive triblock copolymers with two hydrophilic poly(N-isopropylacrylamide) blocks flanking a central hydrophobic poly(?-caprolactone) block were synthesized by atom transfer radical polymerization. Core-shell micellization of the triblock copolymers was inferred from the ¹H NMR spectra derived in two different solvent environments (CDCl₃ and D₂O). The micellar characteristics of these amphiphilic triblock copolymers were studied by pyrene fluorescence techniques, dynamic light scattering and transmission electron microscopy. The critical micelle concentrations of the triblock copolymers were in the range of 4-16 mg/L and the partition coefficients were in the range of 3.10 × 10⁴ to 2.46 × 10⁵. The mean diameters of the micelles, measured by light scattering, were between 90 and 120 nm. The temperature sensitivity of the triblock copolymers was demonstrated by the phase transition of a 250 mg/L aqueous polymer solution at the lower critical solution temperature (LCST). The enthalpy of the phase transition was determined by differential scanning calorimetry. PM3 quantum mechanical calculation method was used to understand the intermolecular interactions between the copolymer and the water molecules. A modular approach was used to simulate the phase transition observed at the LCST.     

Synthesis, reactivity, and pH-responsive assembly of new double hydrophilic block copolymers of carboxymethyldextran and poly(ethylene glycol)

Double hydrophilic block copolymers (DHBC) were prepared by end-to-end coupling of two biocompatible water-soluble homopolymers: the polysaccharide dextran (M_w 8300 or 14,700 g mol⁻¹) and ω-amino poly(ethylene glycol) (PEG-NH₂, M_w 3000 or 7000 g mol⁻¹). The synthesis involved, first, specific oxidation of the dextran terminal aldehyde group and, second, covalent linkage of PEG-NH₂ via a lactone aminolysis reaction. The diblock copolymers dextran-PEG (DEX-PEG) were converted in high yield into the corresponding carboxymethyldextran-PEG (CMD-PEG) derivatives with control over the degree of substitution, from 30 to 85 mol% CH₂COOH groups per glucopyranosyl unit. Further modifications of a CMD-PEG block copolymer led to N-(2-aminoethyl)carbamidomethyldextran-PEG yielding a pair of oppositely-charged DHBC of identical charge density, chain length, and neutral block/charged block content. The properties of CMD-PEG in aqueous solutions were studied by static and dynamic light scattering as a function of solution pH, providing evidence of the pH-sensitive assembly of the copolymers driven by inter- and intra-chain hydrogen-bond formation.