Surface Modification of Titania Nanoparticles Using Ultrathin Ceramic Films

Surface modification of titania nanoparticles was achieved by coating them with ultrathin alumina films using atomic layer deposition. The coating process was performed in a fluidized bed reactor at low pressure and under mechanical vibration. Films were deposited using self-limiting, sequential surface reactions of trimethylaluminum and water. The composition of alumina-coated particles was verified using infrared spectroscopy. The deposited films had an average growth rate of 0.2 nm/coating cycle and were highly uniform and conformal as demonstrated by transmission electron microscopy and X-ray spectroscopy. Deposited alumina films were amorphous as verified through X-ray diffraction and high-resolution electron microscopy. The coating process did not promote particle sintering as validated via particle size and surface area analysis.     

Dynamic mechanical analysis of polymers in the liquid state: Use of a perforated shim stock support

This report summarizes some initial results on the use of a perforated brass shim stock support to extend the useful range of dynamic mechanical testing well over 100 degrees above the traditional limiting polymer softening points of T_g or T_m. Weak secondary relaxations were observed above T_g in both polyisobutylene (PIB) and polystyrene (PS) homopolymer, copolymer, and blend systems and above T_m in gutta percha (trans-polyisoprene). The DuPont 981 Dynamic Mechanical Analyzer (DMA)–990 Thermal Analyzer system was used to characterize these weak liquid state processes. The DMA instrument deforms the specimen in flexure, thus minimizing the shear component present in some other techniques. Specimen-coating weights are typically in the range 20–40 mg. The perforations are particularly useful for polymers having low inherent adhesion to metals or systems which are very brittle in the glassy state, e.g., low MW PS's and many methacrylates.     

Thermomechanical analysis of Tg and T > Tg transitions in polystyrene

Phenomenological softening points were measured on a series of 13 anionic, nearly monodisperse, atactic polystyrenes using a DuPont 943 thermomechanical analyzer (TMA) in a penetration mode. Although TMA cannot identify the nature of the “transition” observed as such, the results obtained support the evidence for the T_g, T_ll, and T′_ll transition in polystyrene discussed in recent literature. T_g and T_ll were found to vary with molecular weight in a systematic manner, while T′_ll could only be observed at very high molecular weight. The technique appears to be quite useful in offering rapid and reproducible information on the various transitions in the liquid state of polystyrene.     

Viscosity index. I. Evaluation of selected copolymers incorporating n-octadecyl acrylate as viscosity index improvers

Compositionally and structurally varied copolymers all containing n-octadecyl acrylate were prepared and evaluated as viscosity index improvers in a common base oil under conditions of low shear. Systems evaluated over a range of copolymer and blend composition were: copolymers of n-octadecyl acrylate with, respectively, methyl methacrylate, 2-ethylhexyl acrylate, and n-dodecyl acrylate; and homopolymers of poly(n-octadecyl acrylate), prepared with a wide range of molecular weights. Properties were compared with those of blends of commercial methacrylate copolymers (acryloids) which had been freed of their entraining liquid. Mixtures of base oil with copolymers of n-octadecyl acrylate and methyl methacrylate, compared at fixed SAE viscosities, were the most efficient of all blends studied. They had the smallest rate of change of viscosity with temperature (as measured by their ASTM slopes), particularly in the composition region of incipient polymer precipitation at room temperature. Efficiency of certain of these composition was somewhat greater than that of the acryloids. A parameter that related concentration and weight-average molecular weight was used to correlate all of the data for ASTM slope and viscosity. Empirical relations developed by using this parameter enabled rheological data to be estimated that agree within 6% of experimental values for the case of thermodynamically good base oil solvents. These data demonstrated the relatively small contributions of copolymer structure to viscosity index improvement.     

Catalytic Combustion of Model Carbon Particles (CPs) over Pt/β-SiC Catalyst

Platinum catalyst supported on a medium surface area -SiC was successfully used for the catalytic combustion of model carbon particles and compared to a catalyst supported on a low surface area -SiC. The -SiC-based catalyst showed no deactivation as a function of cycling tests while a strong deactivation was observed on the -SiC-based catalyst. This deactivation was attributed to the progressive encapsulation of the platinum particles by a layer of silica which built up during the combustion cycle. These results render possible the use of Pt/-SiC catalyst as a diesel carbon particle catalytic filter with continuous regeneration.     

Effects of chemical additives on high-field electromechanical properties of PMN–PT–BT ceramics

A chemical additive method using sol–gel reactions was used to modify the composition and resultant properties of a commercially available 0.96(0.91Pb(Mg_1/3Nb_2/3)O₃–0.09PbTiO₃)–0.04 BaTiO₃ (PMN–PT–BT) ceramic. Without an additional ball-mixing process, several combinations of minor additives such as Fe, Ba, Sr, Zn, and Ti were incorporated by the chemical method. Weak- and high-field characteristics including dielectric properties, induced strain and polarization, and associated hystereses were evaluated for the samples sintered at 1200 °C for 4 h. All properties were found to depend on the chemical additives and temperature. Especially, the temperature dependence of high-field characteristics revealed different behavior from that reported for conventionally prepared samples. For example, the samples containing 0.5 wt.% SrO, 0.5 wt.% ZnO, and 0.5 wt.% TiO₂ did not exhibit a transition to piezoelectric behavior at the temperature expected from the dielectric measurements. Overall, the coating process has been successfully used to modify, and in some cases, enhance the high-field characteristics of PMN-based ceramics for electromechanical uses.     

Synthesis of end-branched poly(ethylene glycol)s by aqueous atom transfer radical polymerization

Summary This article reports the synthesis of novel hydrophilic end-branched poly(ethylene glycol)s, in aqueous media by atom transfer radical polymerization (ATRP). Poly(ethylene glycol)s with molecular weights 10,000 and 16,000 were end-functionalized and used as bifunctional initiators for the polymerization of a poly(ethylene glycol) macromonomer with a molecular weight of 2,000 (PEGMA), either by aqueous ATRP or in a watedmethanol (l/l V/V) mixture. For both macroinitiators a DP of 10 was the target, giving an average of 5 branches in each end. The rates of polymerization were of the same order of magnitude when the polymerizations were initiated by either of the two macroinitiators in watedmethanol (l/l V/V). When a bifunctional oligo(ethy1ene glycol) initiator (M_n = 600) was used to study the polymerization of PEGMA in water/methanol a reduction in the rate of polymerization was observed indicating an influence of the molecular weight of the initiator on the rate of polymerization. Received 25 Maich 2002/Revised 8 November 2002/Accepted 8 November 2002 Correspondence to Jorgen Kops     

Influence of Phenolic acids on microbial populations in the rhizosphere of cucumber

Experiments were conducted to determine whether changes in soil microbial populations that occur in response to additions of certain allelopathic phenolic acids to bulk soil also occur in the rhizosphere. Cucumber seedlings were transplanted into cups containing a nutrient-enriched mixture of Portsmouth B₁, soil and sand and were watered five times (once every 48 hr) with aqueous solutions of ferulic,p-coumaric, or vanillic acid (each at 0, 0.25, or 0.50ol/g soil material). Nutrient solution was applied on alternate days. Leaf growth was suppressed by up to 42% by phenolic acids, but changes in root growth varied with the compound and concentration in solution. Significant increases (over 600% relative to controls) in populations of fast-growing bacteria in the rhizosphere were detected after two but not after five treatments, and increases (400% relative to controls) in numbers of fungal propagules were detected after five treatments. Such increases suggested that chronic exposure to a phenolic acid might resuit in high populations of rhizosphere microorganisms that could metabolize the compounds and thus alter observable responses by the plant. To test this, plants were watered repeatedly with a low-concentration solution of ferulic acid (chronic treatments; 0.0 or 0.1mol/g soil material in one experiment, 0.000 or 0.025imol/g soil material in a second) and then once with a highconcentration solution (acute treatment; 0.0, 0.5, or 1.0mol/g soil material in the first experiment; 0.000, 0.125, or 0.250mol/g soil material in the second).Paper No. 12385 of the Journal Series of the North Carolina Agricultural Research Service, Raleigh, North Carolina. The use of trade names in this publication does not imply endorsement by the North Carolina Agricultural Research Service or the United States Department of Agriculture of the products named, nor criticism of similar ones not mentioned. Acute treatments and some chronic treatments suppressed leaf growth, but results were inconsistent for root growth. Acute treatments increased numbers of several types of bacteria in the rhizosphere but had inconsistent effects on fungi. Chronic treatments had no effect on numbers of bacteria or fungal propagules in the rhizosphere. Furthermore, chronic treatments did not alter responses of plants or microbial populations to the subsequent acute treatment. Results demonstrated that phenolic acids in soil, which must pass through the rhizosphere before interaction with plant roots can occur, alter the microbial ecology of the rhizosphere. However, microbially mediated acclimation of plants to relatively high concentrations of ferulic acid was not observed.     

Equilibrium catalyst from a fluidized catalytic cracking unit separated by metal content by using carbon nanotubes and a biphasic system

During fluid catalytic cracking (FCC) operations FCC catalyst particles become contaminated with various metals. These metals impact FCC performance and currently requires equilibrium catalyst (ECAT) mixtures consisting of a blend of FCC particles with a time spent in the reactor ranging from minutes to several months to be continuously extracted and sold as low value products or sent to landfills. Here a unique method to recycle FCC ECAT particles is presented, which separates ECAT particles by metal content by synthesizing carbon nanotubes and nanofibers on the ECAT particles surface and using a biphasic system. ECAT with low metal content can be sent back to the FCC unit for further use while ECAT with high metal content can be used for other purposes. Further, we show these treated ECAT materials of high metals content will absorb oil on the surface of water and may prove useful for oil spill clean-up applications.