The effect of nanoclays on the nucleation,crystallization, and melting mechanisms of isotactic polypropylene

The influence of organomodified nanoclay (montmorillonite) on the crystallization and melting mechanisms of isotactic polypropylene (iPP) was studied. Films of both neat polymer and clay nanocomposites were prepared after molecular weight optimization through melt extrusion. Products exhibited the tactoidlike morphology since no compatibilizers were used. The effect of introduction of nanoclay within the polymer was studied through isothermal crystallization and linear heating. The results indicated that low nanoclay concentrations induce the formation of the β‐crystalline structure, its formation being inhibited with high nanoclay contents. Dynamic nonisothermal bulk crystallization experiments indicated that nanoclays act as nucleating agents of iPP. Isothermal, bulk crystallization studies indicated that the crystallization process (induction time and crystallization kinetics) is proportionally accelerated by the nanoclay presence. There was also an accelerated formation of secondary crystallization when nanoclays were present in high concentrations. POLYM. ENG. SCI., 47:1889–1897, 2007. © 2007 Society of Plastics Engineers     

Physical properties of polycaproamide/cationic dyeable poly(ethylene terephthalate) polyblended fibers

Polycaproamide (PCA) and cationic dyeable poly(ethylene terephthalate) (CDP) polymers were blended mechanically (in ratios of 75/25, 50/50, and 25/75) in a melt twin‐screw extruder to prepare three PCA/CDP polyblended materials. The blends of PCA and CDP were spun into fibers. The molar ratio of dimethyl 5‐sulfoisophthalate sodium salt for CDP was 2%. This study investigated the physical properties of PCA/CDP polyblended fibers with nuclear magnetic resonance, gel permeation chromatography, gas chromatography, potentiometer, differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), extension stress–strain measurements, density gradient analysis, and rheometry. The experimental results of DSC proved that PCA and CDP formed an immiscible system. In an SEM image of a 50/50 PCA/CDP blend, the morphological aggregation of a larger size, from 3 to 5 μm in diameter, was observed. The rheological behavior of the PCA/CDP polyblended materials exhibited negative‐deviation blends, and the 50/50 blend of the PCA/CDP polyblended fibers showed a minimum tenacity value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1710–1715, 2004     

Self-assembly and crystallization behavior of a double-crystalline polyethylene-block-poly(ethylene oxide) diblock copolymer

The self-assembly and crystallization behavior of a well-defined low molecular weight polyethylene-block-poly(ethylene oxide) (PE-b-PEO) diblock copolymer was studied. The number-average degrees of polymerization for the PE and PEO blocks were 29 and 20, respectively. The molecular weight distribution was 1.04 as determined by size-exclusion chromatography. The PE-b-PEO sample exhibited two melting points at 28.7 and 97.4 °C for the PEO and the PE crystals, respectively. The crystallization of the PE blocks was unconfined, while the crystallization of the PEO blocks was confined between pre-existing PE crystalline lamellae, as demonstrated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) studies. In the fully crystalline state, both PE and PEO blocks formed extended-chain crystals with PE chains tilted ∼22° from the lamellar normal and PEO chains parallel to the lamellar normal, as evidenced by two-dimensional WAXD study of shear-oriented samples. Regardless of hydrogen bonding among hydroxyl chain ends in the PEO blocks, interdigitated, single-crystalline layer morphology was observed for both PE and PEO crystals. The partial crystalline morphology, where the PE crystallizes and the PEO is amorphous, had the same overall d-spacing as the fully crystalline morphology. A double-amorphous PEO layer sandwiched between neighboring PE crystalline layers was deduced based on a chain conformation study using Fourier transform infrared. The confined crystallization kinetics for PEO blocks was investigated by differential scanning calorimetry, which could be explained by a heterogeneous nucleation mechanism. The slower crystallization rate in the PEO-block than the same molecular weight homopolymer was attributed to the effects of nanoconfinement and PEO chains tethered to the PE crystals.     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Deformation behaviour during cold drawing of nanocomposites based on single wall carbon nanotubes and poly(ether ester) copolymers

Relationships between the macroscopic deformation behaviour and microstructure of a pure (PBT-b-PTMO) block copolymer and a polymer nanocomposite (PBT-b-PTMO + 0.2 wt% SWCNT) were investigated by simultaneous small- and wide-angle X-ray scattering (SAXS and WAXS) during tensile deformation using synchrotron radiation. The Young's modulus was found to be 15% higher for the nanocomposite than for the pure block copolymer as well as the yield strength, while the elongation-to-break was less than a half. This different behaviour can be explained by taking into account the different structural features revealed by SAXS and WAXS and thus considering that SWCNT act as anchors in the nanocomposite, sharing the applied stress with the PBT crystals and partially preventing the flexible, non-crystallisable PTMO chains to elongate.     

Acceleration or retardation to crystallization if liquid-liquid phase separation occurs: Studies on a polyolefin blend by SAXS/WAXD, DSC and TEM

Blends of statistical copolymers containing ethylene/hexene (PEH) and ethylene/butene (PEB) exhibited the behavior of upper critical solution temperature (UCST). The interplay between the early and intermediate stage liquid-liquid phase separation (LLPS) and crystallization of the PEH/PEB 50/50 blend was studied by time-resolved simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. Samples were treated by two different quench procedures: in single quench, the sample was directly quenched from 160 °C to isothermal crystallization temperature of 114 °C; while in double quench, the sample was firstly quenched to 130 °C for 20 min annealing, where LLPS occurred, and then to 114 °C. It was found that in the early stage of crystallization, the integrated values of Iq² and crystallinity, X_c, in the double quench procedure were consistently higher than those in the single quench procedure, which could be attributed to accelerated nucleation induced by enhanced concentration fluctuations and interfacial tension. In the late stage of crystallization, some morphological parameters were found to crossover and then reverse, which could be explained by retardation of lamellar growth due to phase separation formed during the double quench procedure. This phenomenon was also confirmed by DSC measurements in blends of different compositions at varying isothermal crystallization temperatures. The crystal lamellar thickness determined by SAXS showed a good agreement with TEM observation. Results indicated that the early stage LLPS in the PEH/PEB blend prior to crystallization indeed dictated the resulting lamellar structures, including the average size of lamellar stack and the stack distribution. There seemed to be little variation of lamellar thickness and long period between the two quenching procedures (i.e., single quench versus double quench).     

A New Geometric Subproblem to Extend Solvability of Inverse Kinematics Based on Screw Theory for 6R Robot Manipulators

Geometric inverse kinematics procedures that divide the whole problem into several subproblems with known solutions, and make use of screw motion operators have been developed in the past for 6R robot manipulators. These geometric procedures are widely used because the solutions of the subproblems are geometrically meaningful and numerically stable. Nonetheless, the existing subproblems limit the types of 6R robot structural configurations for which the inverse kinematics can be solved. This work presents the solution of a novel geometric subproblem that solves the joint angles of a general anthropomorphic arm. Using this new subproblem, an inverse kinematics procedure is derived which is applicable to a wider range of 6R robot manipulators. The inverse kinematics of a closed curve were carried out, in both simulations and experiments, to validate computational cost and realizability of the proposed approach. Multiple 6R robot manipulators with different structural configurations were used to validate the generality of the method. The results are compared with those of other methods in the screw theory framework. The obtained results show that our approach is the most general and the most efficient.

     

液态金属快速结晶的热力学驱动力

采用超高真空无容器悬浮熔炼技术使液态Ｆｅ和Ｎｉ的过冷度分别达２００和２３５Ｋ，借助量热法测定出其比热各为４８．６和４０．５Ｊ·ｍｏｌ~（－１）·Ｋ~（－１）．据此精确计算出深过冷Ｆｅ和Ｎｉ快速结晶的热力学驱动力△Ｇ_（ＬＳ），并与Ｔｕｒｎｂｕｌｌ模型和Ｄｕｂｅｙ－Ｒａｍａｃｈａｎｄｒａｒａｏ模型的近似计算结果相比较，发现这两种近似模型在过冷度超过１００Ｋ时均产生大于１％的偏差．进一步分析发现，△Ｇ_（ＬＳ）的计算偏差对深过冷液态金属中晶体形核率的影响极大，因此快速凝固研究中应尽可能精确计算△Ｇ_（ＬＳ）．     

A high-throughput and high-capacity IPv6 routing lookup system

With the growing number of routing entries, IP routing lookup has become the major performance bottleneck in backbone routers. In this paper, a complete hardware-based routing lookup system is proposed to achieve high-throughput and high-capacity for IPv6. The proposed system is a cache-centric, hash-based architecture that contains a routing lookup application specific integrated circuit (ASIC) and a memory set. A hash function is used to reduce lookup time for the routing table and ternary content addressable memory (TCAM) effectively resolves the collision problem. The gate count of the ASIC, excluding the binary content addressable memory (BCAM), is about 5306 gates, using an in-house 0.18 μm CMOS single-poly six-metal standard cell library. The results of post-layout simulations show that the ASIC operates in 3.6 ns so that the routing lookup system approaches 260 Mega lookups per second (Mlps), which is sufficient for 100 Gbps networks. The memory density is good, with each routing entry requiring only 64 bits. Moreover, the routing table only needs 10.24 KB on-chip BCAM, 20.04 KB off-chip TCAM and 29.29 MB DRAM for 3.6 M routing entries in the proposed system.     

Implementing a diffusion model optimized by a hybrid evolutionary algorithm to forecast notebook shipments

Taiwan computer firms need to forecast trends in notebook shipments. The Bass diffusion model has been successfully applied to describe the empirical adoption curve for many new products and technological innovations. In order to improve the parameter estimates, a hybrid evolutionary algorithm, which couples genetic algorithms (GAs) with particle swarm optimization (PSO), is proposed. This hybrid approach can produce more accurate estimates of the parameters for the Bass diffusion model. In addition, the price index plays an important role in the notebook market. Thus, the modified diffusion model is proposed to investigate the forecasting performance for notebook shipments. The results illustrate that a hybrid approach outperforms other methods such as nonlinear algorithm, GA and PSO in terms of mean absolute percentage error.