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.

Solvent-vapor treatment induced performance enhancement of poly(3-hexylthiophene): methanofullerene bulk-heterojunction photovoltaic cells

The authors report enhanced poly(3-hexylthiophene) (P3HT):methanofullerene (PCBM) bulk-heterojunction photovoltaic cells via 1,2-dichlorobenzene (DCB) vapor treatment and thermal annealing. DCB vapor treatment can induce P3HT self-organizing into ordered structure leading to enhanced absorption and high hole mobility. Further annealing the device at a high temperature, PCBM molecules begin to diffuse into aggregates and together with the ordered P3HT phase form bicontinuous pathways in the entire layer for efficient charge separation and transport. Compared to the control device that is merely annealed, optical absorption, short-circuit current, and power conversion efficiency are increased for the DCB vapor-treated cell.

Achieving perpendicular alignment of rigid polythiophene backbones to the substrate by using solvent-vapor treatment

The rigid backbone of the poly(3-butylthiophene) molecule adopts a perpendicular orientation with respect to the substrate by using a solvent-vapor treatment (see figure). Small and closely contacting spherulites instead of conventional whisker-like crystals are achieved. This could be utilized to improve charge-carrier mobility particularly in the direction normal to the film plane by designing and constructing thick crystalline domains in the functional layer.

Study of controllable aggregation morphology of ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property

We have studied, both experimentally and theoretically, the aggregation morphology of the ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property. Experimental results showed that the micellar morphology changed from spheres to rods and then to vesicles by changing the common solvent from N-N-dimethylformamide (DMF) to dioxane and then to tetrahydrofuran (THF). These controllable aggregates were also obtained by Monte Carlo simulation. The simulative results showed that the solvent property is a key factor that determines the copolymer aggregation morphology. The morphology changed from spheres to rods and then to vesicles by increasing the solvent solubility, corresponding to the change of stretched of the copolymer chains in the micellar cores. This result is in good agreement with the experimental one. Moreover, the simulative results revealed that the end-to-end distant of the ABA triblock copolymer in the vesicle was larger than that in the spheres and rods, indicating that the copolymer chains were more stretched in vesicles than in the spheres and rods. Furthermore, we gave the distribution of the fraction of the chain number with the end-to-end distance. The results indicated that the amount of folded chains is almost the same as that of stretched chains in the vesicle. Although most chains were folded, stretched chains could be found in the rod and sphere micelles.

A reversibly tunable colloidal photonic crystal via the infiltrated solvent liquid-solid phase transition

A reversibly tunable colloidal photonic crystal between two stop bands was realized by a liquid-solid phase transition of liquid infiltrated into the air voids of silica opals. The difference of the peak wavelengths of the two stop bands was dependent on the diameter of the silica opals and the difference of the refractive index of the filled solvent between the solid and liquid state. The reversibly tunable photonic crystals have good stability and reproducibility.

Development of nanodomain and fractal morphologies in solvent annealed block copolymer thin films

We have systematically studied the thin film morphologies of asymmetric polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer subjected to solvent vapors of varying selectivity for the constituent blocks. Upon a short treatment in neutral or PS-selective vapor, the film exhibited a highly ordered array of hexagonally packed, cylindrical microdomains. In the case of PEO selective vapor annealing, such ordered cylindrical microdomains were not obtained. instead, fractal patterns on the microscale were observed and their growth processes investigated. Furthermore, hierarchical structures could be obtained if the fractal pattern was exposed to neutral or PS selective vapor.

Dewetting of polymethyl methacrylate on the patterned elastomer substrate by solvent vapor treatment

The dewetting evolution process of polymethyl methacrylate (PMMA) film on the flat and prepatterned polydimethylsiloxane (PDMS) substrates (with square microwells) by the saturated solvent of methyl ethyl ketone (MEK) treatment has been investigated at room temperature by the optical microscope (OM) and atomic force microscope (AFM). The final dewetting on the flat PDMS substrate led to polygonal liquid droplets, similar to that by temperature annealing. However, on the patterned PDMS substrate, depending on the microwells' structure of PDMS substrate and defect positions that initiated the rupture and dewetting of PMMA, two different kinds of dewetting phenomena, one initiated around the edge of the microwells and another initiated outside the microwells, were observed. The forming mechanism of these two different dewetting phenomena has been discussed. The microwells were filled with liquid droplets of PMMA after dewetting due to the formation of fingers caused by the pinning of the three-phase-line at the edge of the microwells and their rupture.

Solvent extraction of lanthanides and yttrium from nitrate medium with CYANEX 925 in heptane

The extraction behavior of lanthanides and yttrium usinsg CYANEX 925 (mixture of branched chain alkylated phosphine oxides) in n-heptane from nitrate medium has been studied. The effects of aqueous phase ionic strength, CYANEX 925 concentration in the organic phase, and temperature on Sm3+, Nd3+ and Y3+ extraction have been investigated. The extractability of the lanthanides and yttrium increases with increasing nitrate concentration, as well as with increasing CYANEX 925 concentration. An extraction mechanism is proposed based on slope analysis. Furthermore, the infra-red spectra of CYANEX 925 saturated with lanthanides are employed to provide evidence of the composition of the complex. The relationship between the logarithm of the distribution ratio and lanthanide atomic number is also discussed which indicates that yttrium can be separated from fight lanthanides. In addition separation of the light and heavy lanthanide groups is also possible using CYANEX 925. From the temperature dependence data, the thermodynamic parameters values (Delta H, Delta S and Delta G) are calculated.