Extraction and separation of cerium(IV) from nitric acid solutions containing thorium(IV) and rare earths(III) by DEHEHP

The extraction behaviour of Ce(IV), Th(IV) and part of RE(III), viz., La, Ce, Nd and Yb, has been investigated using di(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP,B) in heptane as an extractant. Results show that extractability varies in the order: Ce(IV) > Th(IV) much greater than RE(III). Therefore, it is possible to find the appropriate conditions under which Ce(IV) can be effectively separated from Th(IV) and RE(III). Furthermore, stripping Ce(IV) from the loaded organic phase can be carried out by dilute H2SO4 with an aliquot of H2O2.Roasted bastnasite made in Baotou (China) by Na2CO3 and leached by HNO3, there is about 50% Ce mainly as tetravalent nitrate along with other RE(III) and Th(IV) in the leachings. Through fractional extraction, taking nitric acid leachings of roasted Bastnasite as feed and DEHEHP as an extractant, we can obtain the CeO2 products with high purity of 99.9-99.99%, with a yield of >85%, in which ThO2/CeO2 < 10(-4).

Separation of thorium(IV) and extracting rare earths from sulfuric and phosphoric acid solutions by solvent extraction method

The bastnasite of Baotou (China) was roasted in concentrated sulfuric acid at 250-300 degreesC and the calcined products were leached by water. Almost all rare earths (RE) were moved into solutions in trivalent along with some radioactive impurity thorium(IV) (Th(IV))which accounts for 0.4% of RE and other impurities such as Fe(III), Ca, F, P, etc. Through fractional extraction (seven stages for extraction and nine for scrubbing), the mass ratio of Th(IV) and RE (ThO2/REO) in solution has decreased to 5 x 10(-6). The purity of ThO2 product recovered from organic phase is above 99%. The iron(III) in solutions can be removed in the form of precipitation by adding some magnesia into the solutions. Then RE can be concentrated by solvent extraction with 2-ethylhexyl phosphinic acid 2-ethylhexylester (P-507). The results of fractional extraction show that the concentration of total RE in aqueous solutions stripped by hydrochloric acid is over 200 g REO/I with the yield of RE above 99%. Individual RE can be attained by solvent extraction with P507 in the following process.

Barycenter of energy of lanthanide 4f(N)-(1)5d configuration in inorganic crystals

A semiempirical method for the evaluation of the barycenter of energy of 4f(N-1)5d configurations is presented. The environmental factors affecting the barycenter are given to be the bond volume polarization, fractional covalence of the chemical bond between the central ion and the nearest anion, and presented charge of the nearest anion in the chemical bonds. The barycenter energies of 4f(N-1)5d configurations of Eu2+ and Ce3+ are calculated in various crystals, and the results are in good agreement with the experimental values. A relationship is found between the barycenter of energy of the 4f(N-1)5d configuration on Eu2+ method offers the advantage of applicability to a broad class of luminescence materials and initiates a link between macroscopic properties and microscopic structure.

Structural features of the L-argininamide-binding DNA aptamer studied with ESI-FTMS

The 24-mer DNA aptamer of Harada and Frankel ( Harada, K.; Frankel, A. D. EMBO J. 1995, 14, 5798-5811) that binds L-argininamide (L-Arm) was studied by electrospray ionization Fourier transform mass spectrometry (ESI-FTMS). This DNA folds into a stem and loop such that the loop is able to engulf L-Arm. As controls, two derivatives of the same base composition, one with the same stem but a scrambled loop and the other with no ability to form a secondary structure, were studied. The two DNAs that could fold into stem-loop structures showed a more negatively charged distribution of ions than the linear control. This tendency was preserved in the presence of ligand; complexes expected to have more secondary structure had ions with more negative charges. Distinct species corresponding to no, one, and two bound L-Arm molecules were observed for each DNA. The fractional peak intensities were fit to a straightforward binding model and binding constants were obtained. Thus, ESI-FTMS can provide both qualitative and quantitative data regarding the structure of DNA and its interactions with noncovalent ligands.

Characterization of the microstructure of biaxially oriented polypropylene using preparative temperature-rising elution fractionation

Two commercial biaxially oriented polypropylene (BOPP) resins, resin A and resin B, having different processing properties, were fractionated by preparative temperature-rising elution fractionation (TREF). The TREF fractions were further characterized by gel permeation chromatography (GPC), gel permeation chromatography coupled with light scattering (GPC-LS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). GPC-LS did not find visible long-chain branching in either resin A or B. The results from TREF and DSC indicate that the fractional melting parameter f(T) may be used to predict the profile of the TREF cumulative weight distribution curve. GPC results show that the molecular weights of the fractions tend to increase with elution temperature. WAXD and DSC data show that the crystallinity of fractions does not increase monotonically with increase of elution temperature. There appears to be a maximum in the plot of crystallinity versus elution temperature. The high-speed BOPP resin A has a lower isotacticity but a homogeneous isotacticity distribution and a higher molecular weight but a broader molecular weight distribution than resin B.

Colloid chemical approach to nanoelectrode ensembles with highly controllable active area fraction

A novel "bottom-up" approach to highly controllable nanoelectrode ensembles (NEEs) has been developed using colloidal nanoparticle self-assembly techniques. Ibis solution-based strategy allows flexible control over nanoelectrode size, shape, and interspacing of the as-prepared NEEs. Atomic force microscopy (AFM) was proved to be a powerful tool to monitor the NEE topography, which yields parameters that can be used to calculate the fractional nanoelectrode area of the NEEs. AFM, ac impedance, and cyclic voltammetry studies demonstrate that most of nanoelectrodes on the NEEs (at least by 9-min self-assembly) are not diffusionally isolated under conventional ac frequency range and scan rates. As a result, the NEEs behave as "nanoelectrode-patch" assemblies. Besides, the as-prepared NEEs by different self-assembling times show an adjustable sensitivity to heterogeneous electron-transfer kinetics, which may be helpful to sensor applications. Like these NEEs constructed by other techniques, the present NEEs prepared by chemical self-assembly also exhibit the enhancement of electroanalytical detection limit consistent with NEE theory prediction.

Calculation of chemical bond parameters in La1-xCaxCrO3 (0.0 <= x <= 0.3)

The chemical bond parameters, that is, bond covalency, bond susceptibility, and macroscopic linear susceptibility of La1-xCaxCrO3 (x = 0.0, 0.1, 0.2, 0.3) has been calculated using a semiempirical method. This method is the generalization of the dielectric description theory proposed by Phillips, Van Vechten, Levine, and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. One is the bond valence sums (BVS) scheme, and the other is the equal-valence scheme. Both schemes suggest that for the title compounds bond covalency and bond susceptibility are mainly influenced by bond valence and are insensitive to the Ca doping level or structural change. Larger bond valences usually result in higher bond covalency and bond susceptibility. The macroscopic linear susceptibility increases (only slightly for BVS scheme) with the increasing Ca doping level. (C) 1999 John Wiley & Sons, Inc.

Influence of bond valence on bond covalency in calcium doped lanthanum chromite

The influence of bond valence on bond covalency in La1-xCaxCrO3(x =0.0, 0.1, 0.2, 0.3) has been studied by using semiempirical method. This method is the extension of the dielectric description theory proposed by Phillips, Van Vechten, levine and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. The first is the equal-valence scheme, and the second is Bond Valence Sums (BVS) scheme. Both schemes suggest that for the title compound bond covalency be mainly influenced by bond valence, and insensitive to the Ca doping level. Generally speaking, larger bond valences usually result in higher bond covalencies.

Evaluation of bond covalency and bond valence in Sr-doped perovskite-type compounds

Formulas for decomposing of complex crystals to a sum of binary crystals are described and applied to the study of bond covalency in La1-xSrxFeO3 (0.0 less than or equal to x less than or equal to 0.9) and Ca1-xSrxMnO3 (0.0 less than or equal to x less than or equal to 0.5). The bond valence is treated by bond-valence sums scheme. The results indicate that, for both compounds, with the increasing doping level, the bond covalency and bond valence show the same trend, namely, larger bond covalency corresponds to higher bond valence. For La1-xSrxFeO3, with the increase of doping level, the bond covalency of La-O, Ca-O decreases in the orthorhombic (0.0 less than or equal to x less than or equal to 0.2) and rhombohedral (0.4 less than or equal to x less than or equal to 0.7) systems, then increases slightly for the cubic (0.8 less than or equal to x less than or equal to 0.9) system, but that of Fe-O increases for all crystal systems. A sharp decrease in bond covalency was observed where the crystal changes from orthorhombic to rhombohedral, while a smooth trend was seen for the rhombohedral-to-cubic transition. On the other hand, for orthorhombic Ca1-xSrxMnO3, the bond covalency of Ca-O, Sr-O, and Mn-O (4-coordinate site) decreases with the increasing doping level, that of Mn-O (2-coordinate site) increases.

Gas transport property of homo- and copolyimides from isomeric thiaphthalic dianhydride and oxydianiline

Gas transport properties of home- and copolyimides prepared from 3,3',4,4'- and 2,2',3,3'-thiaphthalic dianhydride (p-TDPA and m-TDPA, respectively) with 4,4-oxydianiline (ODA) were investigated. The fractional free volume of m-TDPA-ODA is larger than that of p-TDPA-ODA, and the chain segmental mobility of the former is lower than that of the latter. The permeability coefficients of m-TDPA-ODA to H-2, CO2, and O-2 are more increased by 48, 69 and 75%, at 30 degrees C and 10 atm, respectively, than those of p-TDPA-ODA; but the permselectivities of m-TDPA-ODA for H-2, CO2, and O-2 toward N-2 are more decreased by 33, 77, and 26%, respectively, than those of p-TDPA-ODA. The permeability coefficients and the diffusion coefficients of the copolyimides can be described by the following equations: log P = Phi(p) log P-p + Phi(m), log P-m and log D-a = D-a = Phi(p) log(D-alpha)(p) + Phi(m) log(D-a)(m), respectively. The variation of the permselectivity is controlled predominantly by diffusivity selectivity. These observations are interpreted in terms of variations in the fractional free volume of polyimides. (C) 1997 John Wiley & Sons, Inc.

X-ray crystallographic structure of meta- and para-dimethyl ester of pyromellitic acid

The polycrystalline powder of para- and meta-dimethyl ester of pyromellitic acid (PMDE) have been prepared by fractional crystallization, and their crystal structures have been determined by Wide-Angle X-ray Diffraction (WAXD). Both p-PMDE and m-PMDE was found to be orthorhombic crystal system, and their unit cell parameters a = 0.840 nm, b = 0.707 nm, c = 1.136 nm and a = 1.032 nm; b = 0.835 nm, c = 0.714 nm, respectively. Space group all belongs to P-mmm. p-PMDE has two molecules per unit cell with crystal density 1.388 g . cm(-3), while m-PMDE has two molecules per unit cell with crystal density 1.522 g . cm(-3). Indices of crystal diffraction peaks are also detailed in the present work. The difference in crystal structures between p-PMDE and m-PMDE has thus been used to explain the curing behavior of isomerically pyromellitic dianhydride-based poly(amic ester)s.

Gas permeation properties of copolyimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride

A series of aromatic copolyimides was prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride (6FDA) with 3,3'-dimethyl-4,4'-methylene dianiline (DMMDA) by a chemical imidization. The gas permeability coefficients of the copolyimides to H-2, CO2, O-2, N-2 and CH4 were measured under 7 atm. pressure. The fractional free volume of 6FDA-DMMDA is larger than that of HQDPA-DMMDA, while the chain segmental mobility of 6FDA-DMMDA is lower than that of HQDPA-DMMDA. The gas permeability of 6FDA-DMMDA is much higher than that of HQDPA-DMMDA but the permselectivity of 6FDA-DMMDA for H-2, CO2, O-2, N-2 over CH4 is lower than that of HQDPA-DMMDA. The experimental values of the gas permeability coefficients of the copolyimides are in satisfactory agreement with the values estimated from the gas permeability coefficients of the constituent homopolyimides and their weight fractions.

Laser light-scattering study of novel thermoplastics .2. Phenolphthalein poly(ether sulfone) (PES-C)

Five narrowly distributed fractions of phenolphthalein poly(ether sulfone) (PES-C) were studied in CHCl3 by both static and dynamic laser light scattering (LLS) at 25 degrees C. The dynamic LLS showed that the PES-C samples contain some large polymer clusters as in previously studied phenolphthalein poly(ether ketone)(PEK-C). These large clusters can be removed by a 0.1-mu m filter. Our results showed that [R(g)(2)](1/2)(z) = (3.35 +/- 0.13) x 10(-2) M(w)((0.52 +/- 0.03)) and [D] = (2.26 +/- 0.02) x 10(-4)M(w)-((0.54) +/- 0.03)) with [R(g)(2)](1/2)(z), M(w) and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.45 +/- 0.04) x 10(-4)M-((0.55 +/- 0.05)), where D and M correspond to monodisperse species. Using this scaling relationship, we have successfully converted the translational diffusion coefficient distribution into the molecular weight distribution for each of the five PES-C fractional The weight-average molecular weights obtained from dynamic light scattering have a good agreement with that obtained from static laser light-scattering measurements.

Deep Fractionation of Clinopyroxene in the East Pacific Rise 13 degrees N: Evidence from High MgO MORB and Melt Inclusions

Mid-ocean ridge basalts (MORBs) from East Pacific Rise (EPR) 13 degrees N are analysed for major and trace elements, both of which show a continuous evolving trend. Positive MgO-Al2O3 and negative MgO-Sc relationships manifest the cotectic crystallization of plagioclase and olivine, which exist with the presence of plagioclase and olivine phenocrysts and the absence of clinopyroxene phenocrysts. However, the fractionation of clinopyroxene is proven by the positive correlation of MgO and CaO. Thus, MORB samples are believed to show a "clinopyroxene paradox". The highest magnesium-bearing MORB sample E13-3B (MgO = 9.52%) is modelled for isobaric crystallization with COMAGMAT at different pressures. Observed CaO/Al2O3 ratios can be derived from E13-3B only by fractional crystallization at pressure > 4 +/- 1 kbar, which necessitates clinopyroxene crystallization and is not consistent with cotectic crystallization of olivine plus plagioclase in the magma chamber (at pressure similar to 1 kbar). The initial compositions of the melt inclusions, which could represent potential parental magmas, are reconstructed by correcting for post-entrapment crystallization (PEC). The simulated crystallization of initial melt inclusions also produce observed CaO/Al2O3 ratios only at > 4 +/- 1 kbar, in which clinopyroxene takes part in crystallization. It is suggested that MORB magmas have experienced clinopyroxene fractionation in the lower crust, in and below the Moho transition zone. The MORB magmas have experienced transition from clinopyroxene+plagioclase+olivine crystallization at > 4 +/- 1 kbar to mainly olivine+plagioclase crystallization at < 1 kbar, which contributes to the explanation of the "clinopyroxene paradox".

Mineral chemistry and its genetic significance of olivine in Cenozoic basalts from the South China Sea

We dredged lots of Cenozoic basalts from areas covered from the northern sub-slope to the southern sub- slope of the South China Sea. Based on the study on mineral chemistry of clinopyroxenes in these Cenozoic hasalts, this paper indicates that pyroxenes are mostly enstatite and a few of augite, sahlite and Ca-rich pyroxene. Pyroxene microlite has higher content in, Ca, Ti and Fe than pyroxene phenocryst, it may reflect that the evolution trend of host magma of pyroxene is coincidence with that of alkali rock series. The depth of magma chambers which calculated from equilibrium temperatures and pressures between clinopyroxene and melt are as follows, that of magma of tephrite is about 49km, that of magma of trachybasalt is about 25km, and that of magma of basalt is about 15km. Correspondingly, Equilibrium temperatures( K) of three types rocks mentioned above gradually decrease from 1535 1498 to 1429 to 1369. By using discriminant plot which developed from pyroxene and alkali discriminant diagram of host rock, Cenozoic basalt from the South China Sea belongs to intraplate alkali basalt. The results suggest that alkali basalt series in the study area may be the products of continuous evolution of mantle plume, which result from some physical and chemistry process including partial melting and fractional crystallization of mantle plume during the course of its ascent to the surface.