Morphology development of ultrathin symmetric diblock copolymer film via solvent vapor treatment

We have followed the time development of the microdomain structure in symmetric diblock copolymer poly(styrene-b-methyl methacrylate), P(S-b-MMA), ultrathin films via PMMA-selective solvent vapor treatment by atomic force microscopy (AFM). After preparation on a substrate preferentially attracting the PMMA block, PS forms a continuous layer at a film's free surface. With subsequent solvent vapor treatment, the film gradually shows a well-ordered hexagonally packed nanocylinders structure. It is shown that only when the film thickness is less than the 1/2L(0) (lamellar repeat spacing), and exposed to PMMA block selective solvent for an appropriate time, can the well-ordered hexagonally packed nanocylinders form. On an extended solvent vapor treatment, a mixed morphology containing nanocylinders and stripes appears, followed by the striped morphologies. When the annealing time is long enough, the film comes back to the flat surface again, however, with PMMA instead of PS dominating the free surface.

The formation of ordered nanoholes in binary, chemically similar, symmetric diblock copolymer blend films

Binary symmetric diblock copolymer blends, that is, low-molecular-weight poly(styrene-block-methyl methacrylate) (PS-b-PMMA) and high-molecular-weight poly(styrene-block-methacrylate) (PS-b-PMA), self-assemble on silicon substrates to form structures with highly ordered nanoholes in thin films. As a result of the chemically similar structure of the PMA and the PMMA block, the PMMA chain penetrates through the large PMA block that absorbs preferentially on the polar silicon substrate. This results in the formation of nanoholes in the PS continuous matrix.

New titanium complexes with two beta-enaminoketonato chelate ligands: Syntheses, structures, and olefin polymerization activities

New titanium complexes with two nonsymmetric bidentate beta-enaminoketonato (N,O) ligands (4a-e), [(Ph)NC(R-2)C(H)C(R-1)O](2)TiCl2, have been synthesized. X-ray crystal structure reveals that complex 4a has a C-2-symmetric conformation with a distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-e are active catalysts for ethylene polymerization at room temperature, producing high molecular weight polyethylenes bearing linear structures. The 4a,b/MMAO catalyst systems exhibit the characteristics of a quasi-living polymerization of ethylene, producing polyethylenes with narrow molecular weight distributions. Moreover, the 4a-d/MMAO catalyst systems are also capable of promoting the quasi-living copolymerization of ethylene with norbornene at room temperature, yielding high molecular weight alternating copolymers with narrow molecular weight distributions. The quasi-living nature of the catalysts allows the synthesis of new A-B polyethylene-block-poly(ethylene-conorbornene) diblock copolymer.

Effect of crystallization on the lamellar orientation in thin films of symmetric poly(styrene)-b-poly(L-lactide) diblock copolymer

The effect of crystallization on the lamellar orientation of poly( styrene)-b-poly(L-lactide) (PS-PLLA) semicrystalline diblock copolymer in thin films has been investigated by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In the melt state, microphase separation leads to a symmetric wetting structure with PLLA blocks located at both polymer/substrate and polymer/air interfaces. The lamellar period is equal to the long period L in bulk determined by small-angle X-ray scattering (SAXS). Symmetric wetting structure formed in the melt state provides a model structure to study the crystallization of PLLA monolayer tethered on glassy (T-c < T-g,T-PS) or rubber (T-c > T-g,T-PS) PS substrate. In both cases, it is found that the crystallization of PLLA results in a "sandwich" structure with amorphous PS layer located at both folding surfaces. For T-c <= T-g,T- PS, the crystallization induces a transition of the lamellar orientation from parallel to perpendicular to substrate in between and front of the crystals. In addition, the depletion of materials around the crystals leads to the formation of holes of 1/2 L, leaving the adsorbed monolayer exposure at the bottom of the holes.

Morphologies in solvent-annealed thin films of symmetric diblock copolymer

We have systematically studied the thin film morphologies of symmetric poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer after annealing to solvents with varying selectivity. Upon neutral solvent vapor annealing, terraced morphology is observed without any lateral structures on the surfaces. When using PS-selective solvent annealing, the film exhibits macroscopically flat with a disordered micellar structure. While PMMA-selective solvent annealing leads to the dewetting of the film with fractal-like holes, with highly ordered nanoscale depressions in the region of undewetted films. In addition, when decreasing the swelling degree of the film in the case of PMMA-selective solvent annealing, hills and valleys are observed with the coexistence of highly ordered nanoscale spheres and stripes on the surface, in contrast to the case of higher swelling degree. The differences are explained qualitatively on the basis of polymer-solvent interaction parameters of the different components.

Morphology and structures of self-assembled symmetric poly(di-n-alkylsilanes)

The self-assembly of poly(di-n-butylsilane) (PDBS) and poly(di-n-hexylsilane) (PDHS) on the surfaces of amorphous carbon and highly oriented pyrolytic graphite (HOPG) have been investigated, respectively. The morphology and structures of these self-assembled thin films were studied by using atomic force microscopy, transmission electronic microscopy, and wide-angle X-ray diffraction. In the case of weak van der Waals interactions between absorbed molecules and substrate, i.e., on amorphous carbon, the self-assembly process was driven by absorbate-absorbate intermolecular interactions. For PDBS with weak absorbate-absorbate intermolecular interactions, the thin film showed organization lacking any measurable preferred orientation on the surface of amorphous carbon. While for PDHS with rigid backbone and strong intermolecular interactions, flat-on lamellae with silicon backbones perpendicular to the surface of amorphous carbon were formed. However, in the case of strong van der Waals interactions between absorbed molecules and substrate, i.e., on HOPG, the self-assembly process was tailored by the balance of absorbate-absorbate intermolecular interactions and molecule-substrate interactions. Both PDHS and PDBS thin films grew into edge-on lamellae on the surface of HOPG, which aligned according to a Mold symmetry.

Synthesis of the first mono(cyclopentadienyl)lanthanide Schiff base complex bearing C-2-symmetric tetradentate ligand: crystal structure of [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2)(mu-THF)(THF)

Reaction of YbCl3 with 3 equimolar CpNa (Cp = cyclopentadienide) in THF, followed by treatment with trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine led to the isolation of first mono(cyclopentadienyl) lanthanide Schiff base complex, [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2) (mu-THF)(THF) (1). The molecular structure of 1 shows that it is a dimer in which the two [(eta(5)-C5H5)Yb(mu-OC20H20N2O)] units connecting via a bridging THF oxygen and two bridging oxygen atoms from Schiff base ligands. (C) 1998 Elsevier Science S.A.

Synthesis and X-ray crystal structure of [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2): Mono(cyclopentadienyl)lanthanide complex bearing a C-2-symmetric tetradentate Schiff-base ligand

Cp2SmCl(THF) reacts with 0.5 equivalent disodium salts of trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine give the title complex [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2) (1). X-ray crystal determination shows that the molecule is a dimer, in which two (eta(5)C(5)H(5))Sm(mu-OC20H20N2O) units are connected via a THF oxygen and two bridging oxygen atoms of Schiff base ligands. The average Sm-C distance is 2.78(7) Angstrom, while those of Sm-O (bridging THF oxygen) and Schiff base oxygens are 2.79(3) and 2.43(4) Angstrom; respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

Laser light scattering studies of soluble high-performance polyimides: Solution properties and molar mass distributions

Two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), in CHCl3 at 25 degrees C have been studied using laser light scattering. We found that the z-average radius of gyration ([R(g)]) can be scaled to the weight-average molecular weight (M(w)) as [R(g)] (nm) = 4.95 x 10(-2)M(w)(0.52) and [R(g)] (nm) = 1.25 x 10(-2)M(w)(0.66) respectively for poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), indicating that poly(ODPA/DMMDA) in CHCl3 at 25 degrees C has a more extended chain conformation than poly(BCPOBDA/DMMDA). Using the wormlike chain model approach, we found that the Flory characteristic ratios (C*) of poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA) are similar to 20 and similar to 31, respectively, indicating that both of them have a slightly extended chain conformation in comparison with typical flexible polymer chains, such as polystyrene, whose C-infinity is similar to 10. A combination of the weight-average molar mass (M(w)) with the translational diffusion coefficient distributions (G(D)) has led to D (cm(2)/s) = 3.53 x 10(-4)M(-0.579) and D (cm(2)/s) = 4.30 x 10(-4)M(-0.613) respectively for two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMTA), in CHCl3 at 25 degrees C. Using these two calibrations, we have successfully characterized the molar mass distributions of the two polyimides from their corresponding G(D)s. The exponents of these two calibrations further confirm that both of the polyimides have a slightly extended coil chain conformation in CHCl3. The chain flexibility difference between these two polyimides has also been discussed.

Clay mineral distributions in the southern Yellow Sea and their significance

To better understand the characteristics of the clay minerals in the southern Yellow Sea, the X-ray quantitative determinations have been carried out for the surface samples obtained from the Yellow Sea. With newly compiled clay mineral synoptic maps, the depositional processes were described for four main clay minerals (illite, chlorite, kaolinite and smectite). The analysis shows that most clay minerals are of terrigenous source with the Huanghe River acting as the major sediment supplier. Besides, the source of muddy sediments in the Yellow Sea was also discussed. As for the central Yellow Sea mud (CYSM), the sediments in its northern part mainly come from the Huanghe River, and those in the rest are of multi-origin. Very similarly, a large amount of sediments in the northern part of the southeastern Yellow Sea Mud (SEYSM) derive from the Keum River and Yeong-san River, while those in the southern part are of multi-origin.

Spatial distributions and seasonal variations of particulate phosphorus in the Jiaozhou Bay in North China

Based oil the measurements of particulate phosphorus (PP) in the Jiaozhou Bay front May 2003 to April 2004, the spatial distribution, seasonal variation and biogeochemical characteristics of PP Were investigated to Understand the fates and roles of phosphorus in the Jiaozhou Bay ecosystem. The Concentration of the total PP ranged from 0. 07 to 2. 09 mu mol/dm(3). The concentration of POP was from 0. 01 to 1. 83 mu mol/dm(3), with all average of with all average of 0. 33 mu mol/dm(3), which accounted for 50. 4% in total PP. In general, file concentrations of IT in surface water show obvious seasonal variations in the Jiaozhou Bay. POP was the highest in spring, which derived front the accumulation of phyto-detritus and was the lowest ill autumn, which was decomposed into seawaters to participate the recycle of phosphorus. PIP was the highest in spring and summer and Was the lowest in autumn and winter. PLP Was Mainly influenced by river input in the inner bay lint POP derived front autochthonous source in the outer bay. Overkill, the concentrations of IT in the inner bay were higher than those in mouth and the Older bay. In the inner bay. the concentrations of IT with the area near the shore were higher than those in the center of the bay. Totally PP showed the decreasing trend with depth especially in spring and winter. The high value of PP emerged in 20 and 10 in Corresponding to summer and autumn, respectively. The changes of POP showed hysteretic effect compared with the changes of Chl a in the investigated year. However, according to the Change of Chl a, the second high value of POP which should be emerged ill October was missing due to the remineralization of POP and participation in the recycle of phosphorus, which lead to the high concentration of orthophosphate in seawaters.

Phytoplankton distributions and their relationship with the environment in the Changjiang Estuary, China

This study was carried out in the Changjiang Estuary from 19 to 26 May 2003. Based on the data collected from 29 stations, including two anchor stations, phytoplankton taxonomic composition, abundance, diurnal variability and spatial distribution were examined. Eighty-seven species, including 54 species of diatoms and 16 red tide causative species, were identified. Average diversity index (H') and evenness (J) values were 1.04 and 0.40, respectively. A bloom in abundance of certain phytoplankton species, especially Prorocentrum dentatum and Skeletoneina costatum, was thought to be the cause of the low diversity index and evenness values. Total phytoplankton abundance averaged 6.75 x 10(5) cells 1(-1), and was much higher than previous investigation carried out in the same month in 1986. Abundance increased seaward showing a distinct spatial difference, and the dominant species varied with salinity. Correlation between phosphorus and abundance further supported the former conclusion that phosphorus is the controlling factor in phytoplankton growth in the Changjiang Estuary where light is not limiting. Based on the relationship between DO, pH and abundance, it is likely that the bloom was caused by rapid in situ growth of phytoplankton with high nutrients and sufficient light. The data also indicated that the duration of the bloom was not long and

Size dependence of biomass spectra and abundance spectra: the optimal distributions

Based on the hypothesis of self-optimization, we derive four models of biomass spectra and abundance spectra in communities with size-dependent metabolic rates. In Models 1 and 2, the maximum diversity of population abundance in different size classes subject to the constraints of constant mean body mass and constant mean respiration rate is assumed to be the strategy for ecosystems to organize their size structure. In Models 3 and 4, the organizing strategy is defined as the maximum diversity of biomass in different size classes without constraints on mean body mass and subject to the constant mean specific respiration rate of all individuals, i.e. the average specific respiration rate over all individuals of a community or group, which characterizes the mean rate of energy consumption in a community. Models 1 and 2 generate peaked distributions of biomass spectral density whereas Model 3 generates a fiat distribution. In Model 4, the distributions of biomass spectral density and of abundance spectral density depend on the Lagrangian multipler (lambda (2)). When lambda (2) tends to zero or equals zero, the distributions of biomass spectral density and of abundance spectral density correspond to those from Model 3. When lambda (2) has a large negative value, the biomass spectrum is similar to the empirical fiat biomass spectrum organized in logarithmic size intervals. When lambda (2) > 0, the biomass spectral density increases with body mass and the distribution of abundance spectral density is an unimodal curve. (C) 2001 Elsevier Science B.V. All rights reserved.