Melt rheology of polylactide/montmorillonite nanocomposites

In this article, the linear and nonlinear shear rheological behaviors of polylactide (PLA)/clay (organophilic‐montmorillonite) nanocomposites (PLACNs) were investigated by an Advanced Rheology Expanded System rheometer. The nanocomposites were prepared by master batch method using a twin‐screw extruder with poly(ε‐caprolactone) (PCL) as a compatibilizer. The presence of org‐MMT leads to obvious pseudo‐solid‐like behaviors of nanocomposite melts. The behaviors caused by the formation of a “percolating network” derived from the reciprocity among the strong related sheet particles. Therefore, the storage moduli, loss moduli, and dynamic viscosities of PLACNs show a monotonic increase with MMT content. Nonterminal behaviors exists in PLACNs nanocomposites. Besides the PLACNs melts show a greater shear thinning tendency than pure PLA melt because of the preferential orientation of the MMT layers. Therefore, PLACNs have higher moduli but better processibility compared with pure PLA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3189–3196, 2007     

Competitive influence of atactic polystyrene and supercritical carbon dioxide on the conformation of syndiotactic polystyrene

The crystallization behavior of miscible syndiotactic polystyrene (sPS) and atactic polystyrene (aPS) blends with different sPS/aPS weight ratios was investigated in supercritical CO₂ by using Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Supercritical CO₂ and aPS exhibited different effects on the conformational change of sPS and competed with each other. Increasing the content of amorphous aPS in the blends made its effect on the conformational change of sPS gradually surpass that of supercritical CO₂. Supercritical CO₂ favored the formation of the helical conformation of sPS in lower temperature range and the all trans planar conformation in higher temperature range, instead of forming the latter one only in higher temperature range in ambient atmosphere. However, increasing aPS content in the blends pushed the range for forming the helical conformation to lower temperature and made the all trans planar conformation dominant in aPS/sPS 25/75 blend after treating in supercritical CO₂ above 60 °C. The all trans planar zigzag conformation was more favorable than the helical conformation after mixing aPS in sPS in supercritical CO₂. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1755–1764, 2007     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Nanostructured polymetallaynes of controlled length: Synthesis and characterization of oligomers and polymers from 1,1′‐bis‐(ethynyl)4,4′‐biphenyl bridging Pt(II) or Pd(II) centers

The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu₃)₂ (C?C? C₆H₄? C₆H₄? C?C? )]_n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR ³¹P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007     

N. Charton,A. Feldermann,A. Theis,M. H. Stenzel,T. P. Davis,C. Barner‐Kowollik,Initiator efficiency of 2,2′‐azobis(isobutyronitrile) in bulk dodecyl acrylate free‐radical polymerizations over a wide conversion and molecular weight range (2004) 42(20) 5170–5179

The original article to which this Erratum refers was published in J Polym Sci Part A: Polym Chem (2004) 42(20) 5170–5179. No abstract.     

N‐{3‐[(2‐Ammonioethyl)amino]propyl}ethane‐1,2‐diaminium tris(trifluoromethanesulfonate): a salt of a folded triply protonated tetramine

The structure of a trifluoromethanesulfonate salt of a nontypical triply protonated linear tetramine, C₇H₂₃N₄³⁺·3CF₃SO₃⁻, with a layered crystal structure is presented. One N atom remains unprotonated. The conformation of the cation is enforced by intra‐ and intermolecular hydrogen bonds. The crystal structure is built of ca 10 Å deep layers, within which cations and anions are hydrogen bonded. Each layer is only weakly bound to its neighbours. This study shows a rare example of an unsymmetrically protonated polyamine and the relation between the lack of protonation, intramolecular hydrogen bonding and the conformation of the cation.     

From the Boltzmann equation to the Stokes‐Fourier system in a bounded domain

We prove that the renormalized solutions of the Boltzmann equation considered in a bounded domain with different types of (kinetic) boundary conditions converge to the Stokes‐Fourier system with different types of (fluid) boundary conditions when the main free path goes to zero. This extends the work of F. Golse and D. Levermore [9] to the case of a bounded domain. © 2003 Wiley Periodicals, Inc.     

Metallothionein as a biomarker for mercury in tissues of rat fed orally with cinnabar

Cinnabar, as one of the most widely used mineral drugs in traditional Chinese medicines, has been proven to have prominent curative effects in clinical use for more than 2000 years. But the safety and toxicity of the drug has been under constant debate in clinic usage. Metallothionein (MT) contains about 30% of cysteine in the molecule, and plays an important detoxification role against heavy metals. In this study, it was used as a biomarker to assess mercurial accumulation in rats fed orally with cinnabar. After feeding rats with cinnabar by gastric gavage at different dosages and at different times, the distribution of heavy metals (including mercury, copper and zinc) and MT was investigated among rat tissues, including liver, kidney, heart, brain, testis and blood. Metals and MT determinations were carried out using inductively coupled plasma mass spectrometry (ICP‐MS) and a modified mercury saturation assay technique respectively. The results indicated that mercury was easily accumulated in the tissues of rats exposed to cinnabar, especially in kidney. For example: at a feeding dosage of 5 g kg^?1 (bw) for 4 weeks, the mercury concentrations in kidney were 13, 8.7, 21.6 and 26 times those in liver, testis, brain and heart respectively; and at 2.5 g kg^?1 (bw) for 2 weeks, the mercury concentrations in kidney were 21, 2.1, 3 and 21 times those in liver, testis, brain and heart respectively. In addition, mercury in kidney and liver of all cinnabar groups was significantly higher than that of the control group (P < 0.01). A high positive correlation observed between MT concentrations and mercury levels in both liver and kidney (R² = 0.9299, P < 0.02 for liver; R² = 0.9923, P < 0.0008 for kidney) indicated that MT could be used as a biomarker for mercury in tissues. Copyright © 2004 John Wiley & Sons, Ltd.     

Indirect boundary element method for unsteady linearized flow over prolate and oblate spheroids and hemispheroidal protuberances

The indirect boundary element method was used to study the hydrodynamics of oscillatory viscous flow over prolate and oblate spheroids, and over hemispheroidal bodies hinged to a plate. Analytic techniques, such as spheroidal coordinates, method of images, and series representations, were used to make the numerical methods more efficient. A novel method for computing the hydrodynamic torque was used, since for oscillatory flow the torque cannot be computed directly from the weightings. Instead, a Green's function for torque was derived to compute the torque indirectly from the weightings. For full spheroids, the method was checked by comparing the results to exact solutions at low and high frequencies, and to results computed using the singularity method. For hemispheroids hinged to a plate, the method for low frequencies was checked by comparing the results to previous results, and to exact solutions at high frequencies. Copyright © 2004 John Wiley & Sons, Ltd.     

Numerical analysis of the rotating viscous flow approaching a solid sphere

A numerical simulation is performed to investigate the flow induced by a sphere moving along the axis of a rotating cylindrical container filled with the viscous fluid. Three‐dimensional incompressible Navier–Stokes equations are solved using a finite element method. The objective of this study is to examine the feature of waves generated by the Coriolis force at moderate Rossby numbers and that to what extent the Taylor–Proudman theorem is valid for the viscous rotating flow at small Rossby number and large Reynolds number. Calculations have been undertaken at the Rossby numbers (R_o) of 1 and 0.02 and the Reynolds numbers (R_e) of 200 and 500. When R_o=O(1), inertia waves are exhibited in the rotating flow past a sphere. The effects of the Reynolds number and the ratio of the radius of the sphere and that of the rotating cylinder on the flow structure are examined. When R_o ? 1, as predicted by the Taylor–Proudman theorem for inviscid flow, the so‐called ‘Taylor column’ is also generated in the viscous fluid flow after an evolutionary course of vortical flow structures. The initial evolution and final formation of the ‘Taylor column’ are exhibited. According to the present calculation, it has been verified that major theoretical statement about the rotating flow of the inviscid fluid may still approximately predict the rotating flow structure of the viscous fluid in a certain regime of the Reynolds number. Copyright © 2004 John Wiley & Sons, Ltd.