Morphology and activity of nanosized NdCl3 catalyst for 1,3‐butadiene polymerization

The binary lanthanide catalyst for 1,3‐butadiene was invented for 40 years ago. However, it has not been employed in commercial application due to its poor solubility and low activity. Nanosized neodymium chloride (NdCl₃) was prepared in tetrahydrofuran (THF) medium through dissolution, chelation, and colloidal formation steps. Anhydrous NdCl₃ was dissolved in THF, and ca. 1.5 THF molecules were coordinated. In the colloidal formation step, THF was slowly replaced with the addition of cyclohexane, and pale blue nuclei, nanosize below 200 nm, were formed. The structural studies for NdCl₃ · xTHF using X‐ray powder diffraction (XRD) and scanning electron microscope (SEM) indicate that high ordered crystallinity is decreased with reduced particle size from trigonal prismatic to porous sphere structure. Nano NdCl₃, obtained as colloidal state in cyclohexane, was activated with Al(iBu)₃ and Al(iBu)₂H at room temperature and employed for 1,3‐butadiene solution polymerization. The nanosized Nd catalysts showed high activity (1.0 ～ 1.3 × 10⁵ g/Nd mol · h), which is comparable to that of the ternary neodymium catalyst Nd(neodecanoate)₃/AlEt₂Cl/Al(iBu)₃. The microstructures of polybutadiene, cis, trans, and vinyl, are about 96.0, 3.5, and 0.5%, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1279–1283, 2005     

Improving multikey Quicksort for sorting strings with many equal elements

Bentley and Sedgewick proposed multikey Quicksort with ‘split-end’ partitioning for sorting strings. But it can be slow in case of many equal elements because it adopted ‘split-end’ partitioning that moves equal elements to the ends and swaps back to the middle. We present ‘collect-center’ partitioning to improve multikey Quicksort in that case. It moves equal elements to the middle directly like the ‘Dutch National Flag Problem’ partitioning approach and it uses two inner loops like Bentley and McIlroy's. In case of many equal elements such as DNA sequences, HTML files, and English texts, multikey Quicksort with ‘collect-center’ partitioning is faster than multikey Quicksort with ‘split-end’ partitioning.     

Binary blends of metallocene polyethylene with conventional polyolefins: Rheological and morphological properties

The rheology and morphology of four sets of binary blends of polyethylene synthesized with metallocene catalysis (metallocene polyethylene: MCPE) with polyolefins prepared using Ziegler‐Natta catalysts have been investigated. The blend systems are MCPE with high density polyethylene (MCPE‐HDPE), polypropylene (MCPE‐PP), poly(propylene‐co‐ethylene) (MCPE‐CoPP), and poly(propylene‐co‐ethylene‐co‐1‐butylene) (MCPE‐TerPP). Cole‐Cole plots [storage melt viscosity (η′) versus loss melt viscosity (η″)], plots of the dynamic storage modulus (G′) versus the dynamic loss modulus (G″), and plots of the log melt viscosity (η*, η′, and η″) versus blend compositions were constructed. The morphology of the blends after microtoming and etching was studied. The phase morphology of MCPE‐HDPE appeared homogeneous, whereas the other three blends were heterogeneous. Rheological and morphological investigations indicated that the MCPE‐HDPE blend was miscible, but the other three blends were immiscible in the melt as well as in the solid state. These observations can be rationalized in terms of the similarity of the chemical structures of the polyolefins.     

Recovery of struvite from animal wastewater and its nutrient leaching loss in soil

Contaminants in swine wastewater were recovered in the form of struvite, a crystal of magnesium ammonium phosphate (MAP), using a newly designed process, and the leaching loss of MAP in soil was examined. The continuous flow process was operated under optimal conditions: 1.0 molar ratio of magnesium (Mg) addition with respect to orthophosphate (OP) and an aeration rate of 0.73 L/L min. Five treatments were performed with three replications for soil pH and nutrient leaching loss tests. It was found that 93% of the OP in the swine wastewater was crystallized, and the MAP crystal formation was verified by X-ray diffraction (XRD) and scanning electron microscope (SEM) analyses. The analyses revealed that the pattern of pH change and N leaching losses for MAP-treated soil were remarkably different from those for fused super phosphate (FSP)-urea-treated soils. The pH levels for the control and FSP-urea-treated soils after a five-week experiment were unchanged or slightly decreased, whereas an increase in pH was observed in the MAP-treated soils. Leaching loss of N was higher in FSP-urea treatments, with MAP treatments showing N losses of only 1.93 and 2.05%, respectively, while FSP-urea treatments showed N losses of 7.82 and 6.47%, respectively, during the same period. Phosphate (P) leaching was very slow in both MAP- and FSP-treated groups.     

Blends of ethylene 1‐octene copolymer synthesized by Ziegler–Natta and metallocene catalysts. II. Rheology and morphological behaviors

The rheological and morphological behaviors of commercially available three binary blends of ethylene 1‐octene copolymer (EOC) regarding the melt index (MI), density and comonomer contents, one component made by the Ziegler–Natta and the other by the metallocene catalysts, were investigated to elucidate miscibility and phase behavior. Miscibility of the EOCs blend in a melt state was related to the value of the MI, density, and comonomer content. If the comonomer contents are similar, then the melt viscosity is weight average value, otherwise it is positively or negatively deviated. The microtomed surface prepared by two different cooling processes—one is fast cooling and the other is slow cooling—indicated that all the blends were not homogenous regardless the density, MI, and comonomer content. The Ziegler–Natta catalyzed EOCs exhibited bigger spherulitic diameter and larger ring space than those of the metallocene EOCs prepared by a cooling process. The blends consisting of similar MI showed banded spherulites with different diameter, whereas the blend consisting of different MI and density takes place of explicit phase separation and phase inversion at 1 : 1 blend composition. The melt rheology appeared to influence the mechanical and film properties in the solid state. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1950–1964, 2000     

Comparing technology convergence of artificial intelligence on the industrial sectors: two-way approaches on network analysis and clustering analysis

Scientometrics - This study investigates technology convergence of AI considering both industrial sectors and technological characteristics with patent data in terms of two-way approaches:...     

Living and non-living Ziegler-Natta catalysts: electronic properties of active site

Most of polymerization reactions with Ziegler catalysts operate through the ‘non-living’ mechanism, whereas lanthanide catalysts show a living-mechanism character. The degree of ‘livingness’ in a polymerization reaction is generally investigated through kinetics and the product analysis rather than by direct analysis of a catalyst. We have developed a new insight for judging the ‘livingness’ in polymerization reaction in aspect of electronical properties of the active chain ends of Li, Ni and Nd catalysts for 1,3-butadiene polymerization using the frontier orbital analysis. The frontier orbitals of the Ni catalyst are different from those of the Li and Nd based catalysts. The HOMO of the Ni catalyst has mostly the d-orbital (Ni) character while the LUMO has the p-orbital (C_α and C_γ atoms) as well as the d-orbital (Ni) character. The π-butenyl coordination at the Ni catalyst is η¹-type but those of the Nd and Li catalysts are η³. The atomic charge (+0.003) on the Ni atom and the atomic charge (−0.14) on C_α of the Ni catalyst are much lower than those of the Nd catalyst (Nd +1.09, C_α −0.56).     

5.8‐inch QHD flexible AMOLED display with enhanced bendability of LTPS TFTs

By applying the curve‐type thin film transistor (TFT) with longitudinal strain, TFT parameters do change little down to the 2R bending. The mobility variation range reduces down to 4% compared with 28% of the line‐type channel with transverse strain. The smaller variation is preferred for a high quality display. We clarified that majority carrier's effective mass and scattering rate are dominant factors influencing the bended TFT's performance, which can be controlled by the strain orientation and channel shape. This understanding and improvement was embedded in the 5.8″ flexible QHD active matrix organic light emitting diode panel with multi edge curvature of Galaxy S8. Through this achievement, we made our flexible premium active matrix organic light emitting diode panels more performable, reliable, and highly productive in small R bending circumstance.     

Alleviation of abnormal NBTI phenomenon in LTPS TFTs on polyimide substrate for flexible AMOLED

This letter investigates the negative‐bias temperature instability (NBTI) behavior of p‐channel low‐temperature polycrystalline silicon thin‐film transistors (LTPS TFTs) on plastic substrate. The measurements reveal that the threshold‐voltage positive shift is highly correlated to the passivation of grain boundary trap states. By applying the established phenomenon such as NBTI recovery and H diffusion from PI substrate, a new model is introduced to explain the mechanism and verified by the experiment. With the thick buffer and bottom metal layer or newly processed PI substrate, we succeeded in adjusting the NBTI behavior of LTPS TFTs on plastic substrate.