Distribution of higher-order structures in injection-molded polypropylenes

Flexural test specimens were injection-molded from six homoisotactic polypropylenes with MFI = 0.49-25.1 dg/min under cylinder temperatures of 200-320°C. Distributions in the flow direction of higher-order structures such as crystallinity X_c, thickness of skin layer, a*-axis-oriented component fraction [A*], and crystalline orientation functions and distributions in the thickness direction of higher-order structures such as X_c, β-crystal contents, [A*], and crystalline orientation functions were studied. These higher-order structures are inhomogeneous in the flow and thickness directions, which strongly influences the product properties such as mechanical and thermal properties. Molecular orientation process in injection molding was theoretically analyzed from a viewpoint of growth of recoverable shear strain at the gate and its relaxation in the cavity, which could considerably well explain the variations in the flow and thickness directions of the quantities such as thickness of the skin layer and crystalline orientation functions which express the degree of molecular orientation.     

Preparation of a Translucent, Conductive, Porous Nanocomposite

A translucent, conductive, porous nanocomposite was designed and prepared by depositing SnO₂ on the inner surfaces of the pores of a porous glass plate and on its outer surface using a chemical vapor deposition method. The porous nanocomposite almost maintained its large surface area and pore volume because the pores remained open after they were deposited with SnO₂. Conductivity between the two outer surfaces of the nanocomposite plate was confirmed for the first time.     

Sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer using H and C NMR

The triad-level sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer was reported in a solvent system of o-chlorophenol/deuterated chloroform mixture (50/50 v/v) at 80 °C using 600 MHz ¹H NMR. The well-resolved alcoholic CH₂ proton peak of the glycol units was observed, which made the detailed sequence analysis possible. The peaks of the cis- and trans-forms of the 1,4-cyclohexanedimethylene glycol units were split into the triad sequence in the chain and could be assigned by a comparison of the spectra with those of homopolymers and by an additional two-dimensional heteronuclear multiple bond correlation observation. The triad sequence distributions centered on 1,4-cyclohexanedimethylene glycol units were determined, which was independent of the cis- and trans-forms of the units and controlled according to Bernoullian statistics.     

Characterization and CO2 sorption properties of poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane‐ co‐3‐methacryloxypropyltris(trimethylsiloxy)silane]

Poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane (MAPOSS)‐co‐3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA)] was synthesized through free radical polymerization. The physical and carbon dioxide (CO₂) sorption properties of the copolymer membranes were investigated in terms of the MAPOSS content. As the MAPOSS content increases, the membrane density increased, suggesting a decrease in the fractional free volume. In addition, the thermal stability was improved with increasing the MAPOSS content. These are because of the polyhedraloligomericilsesquioxane (POSS) units that restrict the high mobility of poly(SiMA) segments. The glass transition temperature, T_g of the copolymers was single T_g based on the differential scanning calorimetry, suggesting that the copolymers were random and not phase separation. Based on the CO₂ sorption measurement, the POSS units play a role in reducing Henry's dissolution by suppressing the mobility of the poly(SiMA) component, while POSS units increase the nonequilibrium excess free volume, which contributes to the Langmuir dissolution. Based on these results, the introduction of MAPOSS unit is one of the effective ways to improved the thermal stability and CO₂ sorption property due to the enhancement of the polymer rigidity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of nitrogen incorporated diamond-like carbon thin films using microwave surface-wave plasma CVD

Nitrogenated diamond-like (DLC:N) carbon thin films have been deposited by microwave surface wave plasma chemical vapor deposition on silicon and quartz substrates, using argon gas, camphor dissolved in ethyl alcohol composition and nitrogen as plasma source. The deposited DLC:N films were characterized for their chemical, optical, structural and electrical properties through X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Raman spectroscopy, atomic force microscope and current–voltage characteristics. Optical band gap decreased (2.7 to 2.4 eV) with increasing Ar gas flow rate. The photovoltaic measurements of DLC:N / p-Si structure show that the open-circuit voltage (V_oc) of 168.8 mV and a short-circuit current density (J_sc) of 8.4 μA/cm² under light illumination (AM 1.5 100 mW/cm²). The energy conversion efficiency and fill factor were found to be 3.4 × 10^{− 4}% and 0.238 respectively.     

A flow simulation for the epoxy casting process using a 3D finite‐element method

A three‐dimensional flow simulation for epoxy casting has been developed. A control‐volume‐based finite‐element method is employed, containing a conservative upwind formulation for the advection terms and equal order interpolations for all variables. This simulation predicts the non‐isothermal and reactive flow behavior under the gravity. The viscosity and reaction‐rate parameters were estimated by using a dynamic rheometer and a differential scanning calorimeter. The predicted flow front advancement and temperature profiles in the calculation domain similar to the mold cavity were in close agreement with the corresponding experimental results. The variation of epoxy surface configuration with flow rate also showed the same tendency between the prediction and the experiment. This simulation seems to be applicable not only to the epoxy casting, but also to other molding processes of various thermoset resins. POLYM. ENG. SCI. 45:364–374, 2005. © 2005 Society of Plastics Engineers.     

Melt-mixing by novel pitched-tip kneading disks in a co-rotating twin-screw extruder

Melt-mixing in twin-screw extruders is a key process in the development of polymer composites. Quantifying the mixing performance of kneading elements based on their internal physical processes is a challenging problem. We discuss melt-mixing by novel kneading elements called “pitched-tip kneading disk (ptKD)”. The disk-stagger angle and tip angle are the main geometric parameters of the ptKDs. We investigated four typical arrangements of the ptKDs, which are forward and backward disk-staggers combined with forward and backward tips. Numerical simulations under a certain feed rate and screw revolution speed were performed, and the mixing process was investigated using Lagrangian statistics. It was found that the four types had different mixing characteristics, and their mixing processes were explained by the coupling effect of drag flow with the disk staggering and pitched-tip and pressure flows, which are controlled by operational conditions. The use of a pitched-tip effectively controls the balance of the pressurization and mixing ability.     

Selectivity and mechanism for skeletal isomerization of alkanes over typical solid acids and their Pt-promoted catalysts

Selectivities for skeletal isomerizations of n-butane and n-pentane catalyzed by typical solid acids such as Cs_2.5H_0.5PW₁₂O₄₀ (Cs2.5), SO₄²⁻/ZrO₂, WO₃/ZrO₂, and H-ZSM-5 and their Pt-promoted catalysts were compared. High selectivities for n-butane and low selectivity for n-pentane were observed over Cs2.5 and SO₄²⁻/ZrO₂, while H-ZSM-5 was much less selective, and WO₃/ZrO₂ was highly selective for both reactions. The Pt-promoted solid acids were usually selective for these reactions in the presence of H₂ except for Pt-H-ZSM-5 for n-butane isomerization. Both the acid strength and pore structure would be factors influencing the selectivity. Mechanism of skeletal isomerization of n-butane was investigated by using 1,4-¹³C₂-n-butane over Cs2.5 and Pt–Cs2.5. It was concluded that n-butane isomerization proceeded mainly via monomolecular pathway with intramolecular rearrangement on Pt–Cs2.5, while it occurred through bimolecular pathway with intermolecular rearrangement on Cs2.5. The higher selectivity on Pt–Cs2.5 would be brought about by the monomolecular mechanism. In the skeletal isomerization of cyclohexane, Pt–Cs2.5/SiO₂ was highly active and selective, while Pt–Cs2.5 was less selective. Control in the acid strength of Cs2.5 by the supporting would be responsible for the high selectivity.     

Electrophoretic Deposition Behavior of Aqueous Nanosized Zinc Oxide Suspensions

The rheological behavior and electrophoretic deposition (EPD) of ZnO nanopowder (nano-ZnO) in aqueous media have been described. A cationic polyelectrolyte (polyethylenimine, PEI) was used to disperse and modify the surfaces of the ZnO nanoparticles. The rheological properties of the ZnO aqueous suspension were investigated by measuring the viscosity versus the pH and amount of dispersant. The EPD processing was conducted via cathodic electrodeposition, using stable suspensions with low viscosity, and the depositional behavior was investigated. Bubble-free nano-ZnO deposits with uniform microstructures were successfully obtained, which was an indication of good sintering behavior.