Controlled synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes

The synthesis of monodisperse nanocrystals is an important topic in the field of nanomaterials not only for practical applications, but also for scientific interest in fundamental research. In this feature article, we mainly focus on synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes, and report some progress made recently in the observation and understanding of nucleation and growth of semiconductor nanocrystals. Firstly, a novel two-phase approach to monodisperse nanocrystals, which is different from the well-established synthesis models, is discussed. We demonstrate that the two-phase approach has a quite lengthy nucleation process, and can be applied to the synthesis of many kinds of binary monodisperse nanocrystals.

Microphase Separation of Mixed Polymer Brushes: Dependence of the Morphology on Grafting Density, Composition, Chain-Length Asymmetry, Solvent Quality, and Selectivity

Microphase separation of binary mixed A/B polymer brushes exposed to different solvents is studied using Single-Chain-in-Mean-Field simulations. Effects of solvent quality and selectivity, grafting density, composition, and chain-length asymmetry are systematically investigated, and diagrams of morphologies in various solvents are constructed as a function of grafting density and composition or chain-length asymmetry. The structure of the microphase segregated morphologies lacks long-range periodic order, and it is analyzed quantitatively Using Minkowski measures.

Nucleation in A/B/AB blends: Interplay between microphase assembly and macrophase separation

We study the interplay between microphase assembly and macrophase separation in A/B/AB ternary polymer blends by examining the free energy of localized fluctuation structures (micelles or droplets), with emphasis on the thermodynamic relationship between swollen micelles (microemulsion) and the macrophase-separated state, using self-consistent field theory and an extended capillary model. Upon introducing homopolymer B into a micelle-forming binary polymer blend A/AB, micelles can be swollen by B. A small amount of component B (below the A-rich binodal of macrophase coexistence) will not affect the stability of the swollen micelles. A large excess of homopolymer, B, will induce a microemulsion failure and lead to a macrophase separation.

Solvent impregnated resin prepared using task-specific ionic liquids for rare earth separation

A novel bifunctional task-specific ionic liquid (TSIL), i.e. [trialkylmethylammonium][sec-nonylphenoxy acetate] ([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin, and the prepared solvent impreganated resin (SIR) was studied for rare earth (RE) separation. Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100]. Adsorption kinetics, adsorption isotherm, separation and desorption of the SIR were also studied.

Extraction and separation of rare earths from chloride medium with mixtures of 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester and sec-nonylphenoxy acetic acid

BACKGROUND: 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (HEHEHP, H(2)A(2)) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec-nonylphenoxy acetic acid (CA100, H2B2) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied.

Controlled phase separation for efficient energy conversion in dye/polymer blend bulk heterojunction photovoltaic cells

Low-cost photovoltaic energy conversion using conjugated polymers has achieved great improvement due to the invention of organic bulk heterojunction. in which the nanoscale phase separation of electron donor and acceptor favors realizing efficient charge separation and collection. We investigated the polymer photovoltaic cells using N, N'-bis(1-ethylpropyl)-3,4,9,10-perylene bis(tetracarboxyl diimide)/poly(3-hexyl thiophene) blend as an active layer. It is found that processing conditions for the blend films have major effects on its morphology and hence the energy conversion efficiency of the resulting devices. By optimizing the processing conditions, the sizes of donor/acceptor phase separation can be adjusted for realizing efficient charge separation and collection. The overall energy conversion efficiency of the photovoltaic cell processed with optimized conditions increases by nearly 40% compared to the normally spin-coated and annealed cell.

Effect of Poly (3-hexylthiophene) Nanofibrils on Charge Separation and Transport in Polymer Bulk Heterojunction Photovoltaic Cells

Crystalline poly (3-hexylthiophene) (P3HT) nanofibrils are introduced into the P3HT: [6, 6]-phenyl C61-butyric acid methyl ester (PCBM) composite films via P3HT preaggregation in solution by adding a small amount of acetone, and the correlation of P3HT nanofibrils and the optoelectronic properties of P3HT:PCBM bulk heterojunction photovoltaic cells is investigated. It is found that the optical absorption and the hole transport or the resulted P3HT:PCBM composite films increase with the increase of the amount of P3HT nanofibrils due to the increased P3HT crystallinity and highly interconnected nanofibrillar P3HT networks. However, it is also found that high contents of crystalline P3HT nanofibrils may restrain PCBM molecules from demixing with the P3HT component that forms electron traps in the active layer. and hence reduce the charge collection efficiency. Small contents of P3HT nanofibrils not only improve the demixing between P3HT and PCBM components, but also enhance the hole transport via crystalline P3HT nanofibrillar networks, resulting in efficient charge collection.

Separation of scandium(III) from lanthanides(III) with room temperature ionic liquid based extraction containing Cyanex 925

The separation of Sc(III) from Y(III), La(III) and Yb(III) in [C(8)mim][PF6] containing Cyanex 925 has been investigated, and is reported in this paper. A cation exchange mechanism of Sc(III) in [C(8)mim][PF6] and Cyanex 925 is proposed by study of the influence of anionic and cationic species on the extraction. The coefficient of the equilibrium equation of Sc(III) was confirmed by slope analysis of log D-Sc vs log [Cyanex 925], and the loading capacity also confirmed the stoichiometry of Cyanex 925 to Sc(III) was close to 3:1. Infrared data for Cyanex 925 saturated with Sc(III) in [C(8)mim][PF6] indicated strong interaction between P=O of Cyanex 925 and Sc(III). In addition, the relationship between log D-Sc and temperature showed that temperature had little influence on the extraction process, and the resulting thermodynamic parameters indicated that an exothermic process was involved.

Suppression of phase separation in PC/PMMA blend film by thermoset oligomer

Phase separation of bisphenol A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) thin blend film is suppressed by addition of solid epoxy oligomer. Epoxy has strong intermolecular interactions with both PC and PMMA, while PC and PMMA are quite incompatible with each other. Consequently, phase separation in the PC/PMMA blend film pushes epoxy to the interface; at the same time, PC and epoxy react readily at the interface to form a cross-linking structure, binding PMMA chains together. Therefore, the interface between PC and PMMA is effectively reinforced, and the PC/PMMA thin blend film is stabilized against phase separation. On the other hand, only an optimal content of epoxy (i.e., 10 wt %) can serve as an efficient interfacial agent. In contrast to the traditional reactive compatibilization, here we observed that the cross-linking structure along the interface is much more stable than block or graft copolymers. Atomic force microscopy (AFM) is used to characterize the morphological changes of the blend films as a function of annealing time. Two-dimensional fast Fourier transform (2D-FFT) of AFM data allows quantitative investigation of the scaling behavior of phase separation kinetics.

Extraction and separation of yttrium from the rare earths with sec-octylphenoxy acetic acid in chloride media

Extraction and separation of yttrium from the rare earths in chloride medium using sec-octylphenoxy acetic acid (CA-12), tri-n-butyl phosphate (TBP) as modifier, in kerosene has been investigated. The separation coefficients, beta, were obtained and the extraction selectivity has been enhanced when compared with that of naphthenic acid. The experimental results indicated that CA-12-TBP system could be employed to separate yttrium, from rare earths. Fractional extraction (15 stages for extraction and 10 stages for scrubbing) was studied, the raffinate of the first stage was abundant in purity yttrium of 99.5%, with a yield of > 95%, percentage of yttrium in the mixture rare earths was less than 5% in the loaded organic phase of the 25th stage and loaded capability was about 0.2 mol/L.

Motion of integrated CdS nanoparticles by phase separation of block copolymer brushes

A new method of reversibly moving US nanoparticles in the perpendicular direction was developed on the basis of the phase separation of block copolymer brushes. Polystyrene-b-(poly(methyl methaerylate)-co-poly(cadmium dimethacrylate)) (PS-b-(PMMA-co-PCdMA)) brushes were grafted from the silicon wafer by surface-initiated atom transfer radical polymerization (ATRP). By exposing the polymer brushes to H2S gas, PS-b-(PMNlA-co-PCdNlA) brushes were converted to polystyrene-b-(poly(methyl methacrylate) -co-poly(methacrylic acid)(CdS)) (PS-b-(PMMA-co-PMAA(CdS))) brushes, in which US nanoparticles were chemically bonded by the carboxylic groups of PMAA segment. Alternating treatment of the PS-b-(PMMA-co-PMAA(CdS)) brushes by selective solvents for the outer block (a mixed solvent of acetone and ethanol) and the inner PS block (toluene) induced perpendicular phase separation of polymer brushes, which resulted in the reversible lifting and lowering of US nanoparticles in the perpendicular direction. The extent of movement can be adjusted by the relative thickness of two blocks of the polymer brushes.

The extraction and separation of Ho, Y, and Er(III) with the mixtures of Cyanex 302 and another organic extractant

The extraction and separation of Ho, Y, and Er(III) with the mixtures of bis(2,4,4-trimetylpentyl)monothiophosphinic acid (Cyanex 302) and another organic extractant, such as acidic organic extractant (di-2-ethylhexyl phosphoric acid P204, 2-ethythexyl phosphoric acid mono-2-ethylhexyl ester P507, di-2-ethylhexyl phosphinic acid P229, and sec-nonylphenoxy acetic acid CA-100), neutral organic extractant (tri-n-butyl phosphate TBP, di-(1-metylheptyl)metyl phosphate P350, and branched trialkylphosphinic oxide Cyanex 925) or primary amine N1923, has been investigated in this paper. The extractability and separation ability for the Ho, Y, and Er with the mixtures of Cyanex 302 and organic extractants has been compared. The synergistic effect of the Ho, Y, and Er extraction with the mixtures of Cyanex 302 and P229, Cyanex 925, CA-100, or N1923 has been explored and the synergistic enhancement coefficients have been calculated. At last, the Y3+ synergistic extraction with the mixtures of Cyanex 302 and CA-100 has been determined and the extracted complex has been deduced.

Thermodynamic behavior and applications of KMnO4 in cerium separation process using cyanex 923

In this work, studies were carried out on the extraction properties of Mn(II) and MnO4- in sulfuric acid medium using Cyanex 923. Effects of different variables on the extraction of Mn(II) and MnO4-, such as the concentrations of acid, the extractant, and the temperature, were investigated. Results indicated that Mn(II) was extracted weakly by Cyanex 923; however, MnO4- could be strongly extracted into the organic phase. The extraction mechanism of MnO4- was proposed, and the influence of MnO4- on the extraction of cerium was identified when KMnO4 as oxidizer added into the bastnasite sulfuric acid leaching liquor. As MnO4- was easier to be extracted into the organic phase than Ce(IV) and then lost its ability for oxidization, a new device was designed to realize sufficient oxidization of cerium from III to IV, and which has been applied to industrialization.

Phase separation of PS/PVME blend films induced by capillary force

The phase behavior of a miscible PS/PVME (80/20, w/w) blend film in a confined geometry has been investigated at the annealing temperature much lower than the low critical solution temperature (LCST) of the blend. When the annealing temperature (52degreesC) is near the glass transition temperature of the blend (51.2degreesC), PVME-rich phase at the air-film surface under a microchannel forms smaller protrusion. When the annealing temperature is increased to 70degreesC, the protruding stripes, which are almost developed, are mainly composed of the mobile PVME-rich phase. These results reveal that the capillary force lead to the enrichment of PVME-rich phase at the air-polymer interface of a PDMS microchannel, that is, the capillary force lithography (CFL) can induce the phase separation of PS/PVME blend films.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.