Solvent extraction of rare earths from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and sec-octylphenoxyacetic acid

The extraction of rare earth elements from chloride medium by mixtures of sec-nonylphenoxy acetic acid (CA100) with bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex301) or bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex302) in n-heptane has been studied. The synergistic enhancement of the extraction of lanthanum (III) by mixtures of CA100 with Cyanex301 has been investigated using the methods of slope analysis and constant mole. The extracted complex of lanthanum (III) is determined. The logarithm of the equilibrium constant is calculated as - 1.41. The formation constants and the thermodynamic functions, Delta H, Delta G, and Delta S have also been determined.

Constructing Thin Polythiophene Film Composed of Aligned Lamellae via Controlled Solvent Vapor Treatment

Thin poly(3-butylthiophene) (P3BT) film composed of aligned lamellae attached to the edge of the original film has been achieved via a controlled solvent vapor treatment (C-SVT) method. The polarized optical microscopy operated at both single-polarization and cross-polarization modes has been used to investigate the alignment of the fiber-like lamellae. A numerical simulation method is used to quantitatively calculate angle distributions of the lamellae deviated from the film growth direction. Prepatterned P3BT film edge acts as nuclei which densely initialize subsequent crystal growth by exhausting the materials transported from the partially dissolved film. The growth of new film upon crystallization is actually a self-healing process where the two-dimensional geometric confinement is mainly responsible for this parallel alignment of P3BT crystals. The solvent vapor pressure should be carefully chosen so as to induce crystal growth but avoid liquid instability which will destroy the continuity of the film.

Solvent Vapor-Induced Self Assembly and its Influence on Optoelectronic Conversion of Poly(3-hexylthiophene): Methanofullerene Bulk Heterojunction Photovoltaic Cells

Nanoscale-phase separation of electron donor/acceptor blends is crucial for efficient charge generation and collection in Polymer bulk heterojunction photovoltaic cells. We investigated solvent vapor annealing effect of poly(3-hexylthiophene) (P3HT)/methanofullerene (PCBM) blend oil its morphology and optoelectronic properties. The organic solvents of choice for the treatment have a major effect oil the morphology of P3HT/PCBM blend and the device performance. Ultraviolet-visible absorption spectro,;copy shows that specific solvent vapor annealing can induce P3HT self-assembling to form well-ordered structure; and hence, file absorption in the red region and the hole transport are enhanced. The solvent that has a poor Solubility to PCBM Would cause large PCBM Clusters and result in a rough blend film. By combining an appropriate solvent vapor treatment and post-thermal annealing of the devices, the power conversion efficiency is enhanced.

Autophobic Dewetting of a Poly(methyl methacrylate) Thin Film on a Silicon Wafer Treated in Good Solvent Vapor

The wettability of thin poly(methyl methacrylate) (PMMA) films on a silicon wafer with a native oxide layer exposed to solvent vapors is dependent on the solvent properties. In the nonsolvent vapor, the film spread on the substrate with some protrusions generated on the film surface. In the good solvent vapor, dewetting happened. A new interface formed between the anchored PMMA chains and the swollen upper part of the film. Entropy effects caused the upper movable chains to dewet on the anchored chains. The rim instability depended on the surface tension of solvent (i.e., the finger was generated in acetone vapor (gamma(acetone) = 24 mN/m), not in dioxane vapor (gamma(dioxane) = 33 mN/m)). The spacing (lambda) that grew as an exponential function of film thickness h scaled as similar to h(1.31) whereas the mean size (D) of the resulting droplets grew linearly with h.

Crystal Growth Transition from Flat-On to Edge-On Induced by Solvent Evaporation in Ultrathin Films of Polystyrene-b-Poly(ethylene oxide)

The transition of lamellar crystal orientation from flat-on to edge-on in ultrathin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) via solvent vapor (toluene) treatment Was investigated. When the as-prepared film was treated in saturated solvent vapor, breakout crystals could form quickly, and then they transformed from square single crystals (flat-on lamellae) to dendrites and finally to nanowire crystals (edge-on lamellae). Initially, heterogeneous nucleation tit the polymer/substrate interface dominated the structure evolution, leading to flat-on lamellar crystals orientation. And the transition from faceted habits to dendrites indicated a transition of underlying mechanism from nucleation-controlled to diffusion-limited growth. As the solvent molecules gradually diffused into the polymer/substrate interface, it will subsequently weaken the polymer-substrate interaction.

Formation of Two Kinds of Hexagonally Arranged Structures in ABC Triblock Copolymer Thin Films Induced by a Strongly Selective Solvent Vapor

An order-order transition (OOT) in the sequence of a hexagonally arranged core-shell cylinder to a double-hexagonally arranged dot in polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that: is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 3.23, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.

N-Methyl-N-Allylpyrrolidinium Based Ionic Liquids for Solvent-Free Dye-Sensitized Solar Cells

We prepared four new ionic liquids consisting of N-methyl-N-allylpyrrolidinium cation in conjunction with anions including iodide, nitrate, thiocyanate, and dicyanamide, respectively, and measured their physical properties of density, viscosity, and conductivity. Owing to the relatively lower melting point of electroactive N-methyl-N-allylpyrrolidinium iodide, in combination with three other nonelectroactive ionic liquids, we could construct solvent-free electrolytes possessing high iodide concentrations for dye-sensitized solar cells. We correlated temperature-dependent electrolyte viscosity with molar conductivity and triiodide mobility through applying an empirical Walden's rule and a modified Stokes-Einstein equation, respectively. We have further found that these anions (nitrate, thiocyanate, and dicyanamide) have different influences on surface states and electron transport in the mesoporous titania film, resulting in different photovoltages and photocurrents of dye-sensitized solar cells.

Synthesis of mesoporous YF3 nanoflowers via solvent extraction route

Mesoporous YF3 nanoflowers were successfully prepared via solvent extraction route. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicated that these nanoflowers with uneven porous architectures had a spherical shape and were consisted of many YF3 nanosheets with a thickness of about 15 not. Energy-dispersive spectroscopy (EDS) analysis was used to check the chemical composition and purity of the products. YF3 nanoflowers had bimodal mesoporous distribution and Brunauer-Emmett-Teller (BET) surface area of 116 m(2)/g.

Synthesis of REF3 (RE = Nd, Tb) nanoparticles via a solvent extraction route

NdF3 and TbF3 nanoparticles were successfully synthesized via a solvent extraction route using Cynex923 (R3P=O). X-ray diffraction (XRD) study showed that pure hexagonal phase NdF3 and pure orthorhombic phase TbF3 could be obtained under the current synthetic conditions. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations indicated that as-obtained NdF3 nanoplates have a diameter of 50-80 nm and thickness of 10-20 nm and TbF3 products have sphere morphologies with diameter from 70 to 170 nm. The driving force for the growth of NdF3 nanoplates could be attributed to the hexagonal crystal structure. The luminescence properties of NdF3 and TbF3 nanoparticles were investigated, which indicated that NdF3 nanoparticles showed typical emission at 888,1064, and 1328 nm and TbF3 nanoparticles showed characteristic emission of Tb3+ (f-f).

Solvent-induced Morphology of the Binary Mixture of Diblock Copolymer in Thin Film: The Block Length and Composition Dependence of Morphology

A series of binary SB blend samples with various overall volume fraction of PS (Phi(PS)) and different discrete distribution of the block length (denoted as d(PS) or d(PB)) were prepared by mixing various asymmetric poly(styrene)-block-poly(butadiene) (SB) block copolymers with a symmetric SB block copolymer. The influences of the external solvent field, composition, and the block length distribution on the morphologies of the blends in the thin films were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The experimental results revealed that after solvent annealing, the interface of the blend thin films depended mainly on the cooperative effects of the annealing solvent and the inherently interfacial curvature of the blends. Upon exposure to the saturated vapor of cyclohexane, which has preferential affinity for the PB block, a "threshold" of Phi(PS) (approximate 0.635-0.707) was found. Below such threshold, the influence of the annealing solvent played an important role on the interfacial curvature of the blend thin film.

Study on the Single Crystals of Poly(3-octylthiophene) Induced by Solvent-Vapor Annealing

Needle-like single crystals of poly(3-octylthiophene) (P3OT) have been prepared by tetrahydrofuran-vapor annealing. The morphology and structure of the crystals were characterized with optical microscopy, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and wide-angle X-ray diffraction. It is observed that the P3OT molecules are packed with the backbones parallel to the length axis of the crystal and the alkyl side chains perpendicular to the substrate. The field effect transistor based on the P3OT single crystal exhibited a charge carrier mobility of 1.54 x 10(-4) cm(2)/(Vs) and on/off current ratio of 37, and the molecular orientation of the crystal is ascribed to account for the device performance. The time-dependent morphological evolution demonstrated that the crystals underwent Ostwald ripening when annealed.

SOLVENT AND SUBSTITUENT EFFECTS ON THE INTRAMOLECULAR AMIDE HYDROLYSIS OF N-METHYLMALEAMIC ACID

Intramolecular amide hydrolysis of N-methylmaleamic acid is revisited at the B3LYP/6-311G(2df,p)//B3LYP/6-31G(d,p)+ZVPE level, including solvent effects at the CPCM-B3LYP/6-311G(2df,p)//Onsager-B3LYP/6-31G(d,p)+ZPVE level. The concerted reaction mechanism is energetically favorable over stepwise reaction mechanisms in both the gas phase and solution. The calculated reaction barriers are significantly lower in solution than in the gas phase. In addition, it is concluded that the substituents of the four N-methylmaleamic acid derivatives considered herein have a significant effect on the gas-phase reaction barriers but a smaller, or little, effect on the barriers in solution.

Rim instability by solvent-induced dewetting

We study the condition of the occurrence of the rim instability in the solvent-induced dewetting process. Our experimental results show that the film thickness not only greatly influences the occurrence of the rim instability, but also influences the wavelength lambda as characterized by the undulation of the deformed contact line. The molecular weight of polymer does not almost influence the occurrence of the rim instability and the wavelength lambda. The wavelength lambda is proportional to the width of the rim in the rim instability region. The receding contact angle theta of polymer solutions on substrates in the dewetting process is an important factor to influence the rim instability in the solvent-induced dewetting.

Solvent effects on spectrophotometric titrations and vibrational spectroscopy of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin in aqueoius DMF

The spectrophotometric titration by sodium hydroxide of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin ((OH)(1)PH2) is studied as a function of solvent composition of DMF-H2O binary solvent mixture ([OH-] = 0.04 M). Combining the structure changes of the porphyrin and the "four orbital" model of Gouterman, many features of the optical spectra of this deprotonated para-hydroxy-substituted tetraphenylporphyrin in different composition of binary solvent mixtures can be rationalized. In highly aqueous solvents, the changes of the titration curves are shown to be mainly due to hydrogen-bonding of the oxygen of the phenoxide anion group by the hydroxylic solvent, Which decreases the energy of the phenoxide anion pi orbital. Thus the phenoxide anion pi orbital cannot cross over the porphyrin Tr orbital being a different HOMO. However, its energy is close to that of the porphyrin pi orbitals. As a result, in the visible region, no charge-transfer band is observed, while in the visible-near region, the Soret peak split into two components. In nonaqueous solvents, the changes are mainly attributed to further deprotonation of pyrrolic-Hs of (OH) 1PH2 by NaOH and coordination with two sodium ions to form the sodium complex of (OH) 1PH2, which turns hyperporphyrin spectra of deprotonated of phenolic-H of (OH)(1)PH2 into three-banded spectra of regular metalloporphyrin.