Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

Microstructure and Densification of Pressureless-Sintered Al2O3/Si3N4-Whisker Composites

Composite densification was studied by performing slip casting and sintering experiments on an Al₂O₃ matrix and Si₃N₄ whisker system. Even though all the slip-cast powder compacts exhibited high green densities (up to 70% of the theoretical) and narrow pore-size distribution (pore radius around 15 to 30 nm), significant differential densification on a microscopic scale was found due to the existence of local whisker agglomeration. The inhomogeneous whisker distribution resulted in a binary mixture of large and small pores in the sintered composites, in which whisker-associated flaws remained stable even after prolonged sintering. The sintered microstructures showed that the spatial distribution as well as the volume fraction of the Si₃N₄ affect composite densification. Inhomogeneous whisker distribution dominated the complete densification of the composites.     

Accumulation and Toxicity of Superparamagnetic Iron Oxide Nanoparticles in Cells and Experimental Animals

The uptake and distribution of negatively charged superparamagnetic iron oxide (Fe₃O₄) nanoparticles (SPIONs) in mouse embryonic fibroblasts NIH3T3, and magnetic resonance imaging (MRI) signal influenced by SPIONs injected into experimental animals, were visualized and investigated. Cellular uptake and distribution of the SPIONs in NIH3T3 after staining with Prussian Blue were investigated by a bright-field microscope equipped with digital color camera. SPIONs were localized in vesicles, mostly placed near the nucleus. Toxicity of SPION nanoparticles tested with cell viability assay (XTT) was estimated. The viability of NIH3T3 cells remains approximately 95% within 3–24 h of incubation, and only a slight decrease of viability was observed after 48 h of incubation. MRI studies on Wistar rats using a clinical 1.5 T MRI scanner were showing that SPIONs give a negative contrast in the MRI. The dynamic MRI measurements of the SPION clearance from the injection site shows that SPIONs slowly disappear from injection sites and only a low concentration of nanoparticles was completely eliminated within three weeks. No functionalized SPIONs accumulate in cells by endocytic mechanism, none accumulate in the nucleus, and none are toxic at a desirable concentration. Therefore, they could be used as a dual imaging agent: as contrast agents for MRI and for traditional optical biopsy by using Prussian Blue staining.     

Ultrasonic Spray Pyrolysis for Synthesis of Spherical Zirconia Particles

This paper presents new findings on ultrasonic spray pyrolysis of zirconium hydroxyl acetate precursor drops whose sizes were precisely measured using laser light diffraction technique. Precursor concentration plays a predominant role in determination of product particle size. At 0.01 wt% precursor concentration, conventional spray pyrolysis at 750°C using precursor drops 5–8 μm in diameter, generated by an ultrasonic nebulizer at 2.66 MHz, yielded uniform spherical yttria-stabilized zirconia (YSZ) particles 73 nm in diameter measured by scanning electron microscopy. The YSZ particle diameters were much smaller than those predicted by the one-particle-per-drop mechanism. Under similar reaction conditions, the high-throughput ultrasound-modulated two-fluid (UMTF) spray pyrolysis of larger precursor drops (28-μm peak diameter) also yielded spherical dense particles; they were significantly smaller in size than those produced by the low-throughput conventional ultrasonic spray pyrolysis of smaller drops (6.8-μm peak diameter).     

Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry     

Caffeic Acid Phenethyl Ester Is a Potential Therapeutic Agent for Oral Cancer

Head and neck cancers, which affect 650,000 people and cause 350,000 deaths per year, is the sixth leading cancer by cancer incidence and eighth by cancer-related death worldwide. Oral cancer is the most common type of head and neck cancer. More than 90% of oral cancers are oral and oropharyngeal squamous cell carcinoma (OSCC). The overall five-year survival rate of OSCC patients is approximately 63%, which is due to the low response rate to current therapeutic drugs. In this review we discuss the possibility of using caffeic acid phenethyl ester (CAPE) as an alternative treatment for oral cancer. CAPE is a strong antioxidant extracted from honeybee hive propolis. Recent studies indicate that CAPE treatment can effectively suppress the proliferation, survival, and metastasis of oral cancer cells. CAPE treatment inhibits Akt signaling, cell cycle regulatory proteins, NF-κB function, as well as activity of matrix metalloproteinase (MMPs), epidermal growth factor receptor (EGFR), and Cyclooxygenase-2 (COX-2). Therefore, CAPE treatment induces cell cycle arrest and apoptosis in oral cancer cells. According to the evidence that aberrations in the EGFR/phosphoinositide 3-kinase (PI3K)/protein kinase B (Akt) signaling, NF-κB function, COX-2 activity, and MMPs activity are frequently found in oral cancers, and that the phosphorylation of Akt, EGFR, and COX-2 correlates to oral cancer patient survival and clinical progression, we believe that CAPE treatment will be useful for treatment of advanced oral cancer patients.     

Effect of polyvinylpyrrolidone on morphology and structure of In2O3 nanorods by hydrothermal synthesis

Indium oxide (In₂O₃) nanorods were hydrothermally synthesized from aqueous InCl₃ solution in urea with addition of polyvinylpyrrolidone (PVP) as a steric stabilizer. Indium hydroxide, In(OH)₃, was precipitated at 60 °C and was changed into a transient InOOH phase upon calcination at 250 °C in air. X-ray diffractometry revealed that the existence of PVP delays the phase transformation of InOOH. Cubic-structured In₂O₃ phase was then formed when temperature was raised to 350 °C, regardless of the PVP concentration. The In(OH)₃ phase without the PVP showed a rod-based, flower-like morphology of polycrystalline character. Minor addition of the PVP, i.e., 0.1–2 wt.%, resulted in a pronounced evolution in morphology from the three-dimensional, flower-like form to discrete, one-dimensional nanorods aligned in planar form. Both the flower-like and discrete nanorod morphologies were preserved after heat treatments at 250 and 350 °C. This reveals that the morphological change is attributable to preferential adsorption of the PVP molecules on the In(OH)₃ crystallite surface, so that the aggregate attachment responsible for the multipod growth is inhibited.     

A Novel Technique for Synthesizing Nanoshell Hollow Alumina Particles

A novel and versatile synthesis route has been developed to fabricate hollow Al₂O₃ microspheres with nanoporous shell structures. The method involves a preferential "implantation" of Al species into polymeric template particles to form a core–shell structure in solvent. The template cores can then be removed by thermal pyrolysis to form hollow interiors. This unique "implantation" process allows for synthesis of monodisperse hollow spheres with a nonaggregated character. The implantation of Al species is confirmed by electron spectroscopy for chemical analysis/Auger analysis in depth profiles. The shell structure changes from amorphous to γ-Al₂O₃ at 900°C; because of which, the shell is nanoporous in structure. The porous shell then transforms to α-Al₂O₃ as temperature is further raised above 1000°C. Transmission electron microscopy examination reveals a uniform shell thickness of ca. 20–40 nm, and grain growth appears to be constrained by the thin shell walls at 1100°C, leading to void formation at the triple grain junctions.     

Finite element modeling of segmental chip formation in high-speed orthogonal cutting

An explicit, Lagrangian, elastic-plastic, finite element code has been modified to accommodate chip separation, segmentation, and interaction in modeling of continuous and segmented chip formation in highspeed orthogonal metal cutting process. A fracture algorithm has been implemented that simulates the separation of the chip from the workpiece and the simultaneous breakage of the chip into multiple segments. The path of chip separation and breakage is not assigned in advance but rather is controlled by the state of stress and strain induced by tool penetration. A special contact algorithm has been developed that automatically updates newly created surfaces as a result of chip separation and breakage and flags them as contact surfaces. This allows for simulation of contact between tool and newly created surfaces as well as contact between simulated chip segments. The work material is modeled as elastic/perfectly plastic, and the entire cutting process from initial tool workpiece contact to final separation of chip from workpiece is simulated. In this paper, the results of the numerical simulation of continuous and segmented chip formation in orthogonal metal cutting of material are presented in the form of chip geometry, stress, and strain contours in the critical regions.     

The comparison between the polyol process and the impregnation method for the preparation of CNT-supported nanoscale Cu catalyst

Carbon nanotubes (CNTs) are relatively potential materials for catalyst supports. CNT-supported Cu catalysts were prepared by an impregnation method and a polyol process. The catalytic activity was examined under different reaction atmospheres, Cu contents, and sizes of supports for CO oxidation. The experimental results showed that the active phase on the catalyst prepared by the impregnation method (10–20 nm) was smaller than that on the catalyst prepared by the polyol process (30–50 nm). Furthermore, the smaller active phase showed better performance for CO oxidation. Therefore, catalysts prepared by the impregnation method had a lower activation energy (57.47 kJ mol^?1) than those prepared by the polyol process. The optimum CNT-supported Cu catalyst prepared by the impregnation method using 10–20 nm CNTs had a Cu content of 13.4 wt.%, and a CO conversion of 33% achieved at 125 °C with a total space velocity of 1.56 × 10⁵ h^?1.