Simulation of precipitation reactions in reverse micelles

Precipitation involving mixing of two sets of reverse micellar solutions-containing a reactant and precipitant respectively-has been analyzed. Particle formation in such systems has been simulated by a Monte Carlo (MC) scheme (Li, Y.; Park, C. W. Langmuir 1999, 15, 952), which however is very restrictive in its approach. We have simulated particle formation by developing a general Monte Carlo scheme, using the interval of quiescence technique (IQ). It uses Poisson distribution with realistic, low micellar occupancies of reactants, Brownian collision of micelles with coalescence efficiency, fission of dimers with binomial redispersion of solutes, finite nucleation rate of particles with critical number of molecules, and instantaneous particle growth. With the incorporation of these features, the previous work becomes a special case of our simulation. The present scheme was then used to predict experimental data on two systems. The first is the experimental results of Lianos and Thomas (Chem. Phys. Lett. 1986, 125, 299, J. Colloid Interface Sci. 1987, 117, 505) on formation of CdS nanoparticles. They reported the number of molecules in a particle as a function of micellar size and reactant concentrations, which have been predicted very well. The second is on the formation of Fe(OH)(3) nanoparticles, reported by Li and Park. Our simulation in this case provides a better prediction of the experimental particle size range than the prediction of the authors. The present simulation scheme is general and can be applied to explain nanoparticle formation in other systems.

How the development of condensation particle counters is reforming our view on atmospheric nucleation

Aerosol particles deteriorate air quality, atmospheric visibility and our health. They affect the Earth s climate by absorbing and scattering sunlight, forming clouds, and also via several feed-back mechanisms. The net effect on the radiative balance is negative, i.e. cooling, which means that particles counteract the effect of greenhouse gases. However, particles are one of the poorly known pieces in the climate puzzle. Some of the airborne particles are natural, some anthropogenic; some enter the atmosphere in particle form, while others form by gas-to-particle conversion. Unless the sources and dynamical processes shaping the particle population are quantified, they cannot be incorporated into climate models. The molecular level understanding of new particle formation is still inadequate, mainly due to the lack of suitable measurement techniques to detect the smallest particles and their precursors. This thesis has contributed to our ability to measure newly formed particles. Three new condensation particle counter applications for measuring the concentration of nano-particles were developed. The suitability of the methods for detecting both charged and electrically neutral particles and molecular clusters as small as 1 nm in diameter was thoroughly tested both in laboratory and field conditions. It was shown that condensation particle counting has reached the size scale of individual molecules, and besides measuring the concentration they can be used for getting size information. In addition to atmospheric research, the particle counters could have various applications in other fields, especially in nanotechnology. Using the new instruments, the first continuous time series of neutral sub-3 nm particle concentrations were measured at two field sites, which represent two different kinds of environments: the boreal forest and the Atlantic coastline, both of which are known to be hot-spots for new particle formation. The contribution of ions to the total concentrations in this size range was estimated, and it could be concluded that the fraction of ions was usually minor, especially in boreal forest conditions. Since the ionization rate is connected to the amount of cosmic rays entering the atmosphere, the relative contribution of neutral to charged nucleation mechanisms extends beyond academic interest, and links the research directly to current climate debate.

Study of the growth of capped ZnO nanocrystals: A route to rational synthesis

We report the study of complex and unexpected dependencies of nanocrystal size as well as nanocrystalsize distribution on various reaction parameters in the synthesis of ZnO nanocrystals using poly(vinyl pyrollidone) (PVP) as a capping agent. This method establishes a qualitatively different growth mechanism to the anticipated Ostwald ripening behavior. The study of size-distribution kinetics and an understanding of the observed non-monotonic behaviors provides a route to rational synthesis. We used a simple, but accurate, approach to estimate the size-distribution function of nanocrystals from the UV-absorption spectrum. Our results demonstrate the accuracy and generality of this approach, and we also illustrate its application to various semiconducting nanocrystals, such as ZnO, ZnS, and CdSe, over a wide size range (1.8-5.3 nm).

Mechanical Properties of Al-Mica Particulate Composite Material

Cast aluminium alloy mica particle composites of varying mica content were tested in tension, compression, and impact. With 2.2 percent mica (size range 40µm – 120µm) the tensile and compression strengths of aluminium alloy decreased by 56 and 22 percent, respectively. The corresponding decreases in percent elongation and percent reduction are 49 and 39 percent. Previous work [2] shows that despite this decrease in strength the composite with 2.5 percent mica and having an UTS of 15 kg/mm2 and compression strength of 28 kg/mm2 performs well as a bearing material under severe running conditions. The differences in strength characteristics of cast aluminium-mica particle composites between tension and compression suggests that, as in cast iron, expansion of voids at the matrix particle interface may be the guiding mechanism of the deformation. SEM studies show that on the tensile fractured specimen surface, there are large voids at the particle matrix interface.

Nitride synthesis using ammonia and hydrazine - a thermodynamic panorama

Because of the wide variety of projected applications of ultrapure nitrides in advanced technologies, there is interest in developing new cost-effective methods of synthesis. Explored in this study is the use of ammonia and hydrazine for the synthesis of nitrides from oxides, sulfides and chlorides. Even when the standard Gibbs energy change for the nitridation reactions involved are moderately positive, the reaction can be made to proceed by lowering the partial pressure of the product gas below its equilibrium value. Use of a metastable form of precursor in the nanometric size range is an alternative method to facilitate nitridation. Ellingham-Richardson-Jeffes diagrams are used for a panoramic presentation of the driving force for each set of reactions as a function of temperature. Oxides are the least promising precursors for nitride synthesis; sulfides offer a larger synthetic window for many useful nitrides such as BN, AlN, InN, VN, TiN, ThN and Si3N4. The standard Gibbs free energy changes for reactions involving chlorides with either ammonia or hydrazine are much more negative. Hydrazine is a more powerful nitriding agent than ammonia. The metastability of hydrazine requires that it be introduced into a reactor through a water-cooled lance. The use of volatile halides with ammonia or hydrazine offers the potential for synthesis of pure and doped nanocrystalline nitrides. Nitride thin films can also be prepared by suitable adaptations of the chloride route. (C) 2002 Kluwer Academic Publishers.

Monodisperse sub-10 nm gold nanoparticles by reversing the order of addition in Turkevich method - The role of chloroauric acid

The Turkevich method for synthesizing gold nanoparticles, using sodium citrate as the reducing agent, is renowned for its ability to produce biocompatible colloids with mean size >10 nm. Here we show that monodisperse gold nanoparticles in the 5-10 nm size range can be synthesized by simply reversing the order of addition of reactants, i.e. adding chloroauric acid to citrate solution. Kinetic studies and electron microscopic characterization revealed that the reactivity of chloroauric acid, initial molar ratio of citrate to chloroauric acid (MR), and reaction mixture pH play an important role in producing monodisperse gold nanoparticles. Reversing the order of addition also enhanced the stabilization of nanoparticles at high MR values. Remarkably, the system exhibits a `memory' of the order of addition, even when the timescale of mixing is much shorter than the timescale of synthesis. (C) 2011 Elsevier Inc. All rights reserved.

Densification studies on amorphous ZrO2-Al2O3 powders

Densification characteristics of amorphous ZrO2-40 mol% Al2O3 powder with 3 to 15 mu m nominal particle size range, produced by spray pyrolysis, have been studied by conducting hot pressing experiments at 573, 723 and 873 K with uniaxial pressures of 250, 500 and 750 MPa. Most of the increase in relative density from the starting value of similar to 40% occurred during loading up to the desired pressure. The increments in density during 1 hour constant pressure dwells were less than 4% at all temperatures and pressure. Inter-particle bonding was not observed at 573 K. Correlation between the results with a viscous sintering model for hot pressing is not satisfactory for describing the behavior as normal viscous sintering.

Unusual aerosol characteristics at Challakere in Karnataka

During a series of measurements, simultaneous measurements were made of spectral aerosol optical depths (AOD), black carbon (BC) mass concentration, total and size segregated composite aerosol mass concentrations at the second campus of Indian Institute of Science (IISc), Challakere, Karnataka. Surprisingly, most of the aerosol mass is found in the submicron size range, which is unusual for a dry region. Unexpectedly large enhancement in BC aerosol concentration was observed during the morning hours (6-8 a.m.), both during summer and winter, which is mysterious and hence requires further study. However, BC mass fraction, which is one of the most important climate-relevant parameters was 3.3% of total aerosol mass, implying a significantly low aerosol-induced absorption of solar radiation and hence consequent atmospheric warming. Based on our initial measurements as well as 11 years of satellite data analysis, we conclude that this location is best suited for establishing a climate observatory.

Intracellular delivery of doxorubicin encapsulated in novel pH-responsive chitosan/heparin nanocapsules

A novel polyelectrolyte nanocapsule system composed of biopolymers, chitosan and heparin has been fabricated by the layer-by-layer technique on silica nanoparticles followed by dissolution of the silica core. The nanocapsules were of the size range 200 +/- 20 nm and loaded with the positively charged anticancer drug doxorubicin with an efficiency of 89%. The loading of the drug into the capsule happens by virtue of the pH-responsive property of the capsule wall, which is determined by the pKa of the polyelectrolytes. As the pH is varied, about 64% of the drug is released in acidic pH while 77% is released in neutral pH. The biocompatibility, efficiency of drug loading, and enhanced bioavailability of the capsule system was confirmed by MTT assay and in vivo biodistribution studies.

Taming of large diameter triaxial setup

Triaxial tests are essential to estimate the shear strength properties of the soil or rock. Normally triaxial tests are carried out on samples of 38 mm diameter and 76 mm height. Granular materials, predominantly used in base/sub-base construction of pavements or in railways have size range of 60-75 mm. Determination of shear strength parameters of those materials can be made possible only through triaxial tests on large diameter samples. This paper describes a large diameter cyclic triaxial testing facility set up in the Geotechnical Engineering lab of Indian Institute of Science. This setup consists of 100 kN capacity dynamic loading frame, which facilitates testing of samples of up to 300 mm diameter and 600 mm height. The loading ram can be actuated up to a maximum frequency of 10 Hz, with maximum amplitude of 100 mm. The setup is capable of carrying out static as well as dynamic triaxial tests under isotropic, anisotropic conditions with a maximum confining pressure of 1 MPa. Working with this setup is a difficult task because of the size of the sample. In this paper, a detailed discussion on the various problems encountered during the initial testing using the equipment, the ideas and solutions adopted to solve them are presented. Pilot experiments on granular sub-base material of 53 mm down size are also presented.

Facile hydrothermal synthesis of carbon nanoparticles and possible application as white light phosphors and catalysts for the reduction of nitrophenol

We report a simple hydrothermal synthesis of highly reproducible carbon nanoparticles in a size range between 2 and 7 nmfroma single precursor sucrose without either surface passivating agents or acids and bases. The carbon nanoparticles can be used as white light phosphors, especially for ultraviolet light emitting diodes and metal-free catalyst for the reduction of nitrophenol.

Development, in vitro and in vivo characterization of zoledronic acid functionalized hydroxyapatite nanoparticle based formulation for treatment of osteoporosis in animal model

We investigated the potential of using novel zoledronic acid (ZOL)-hydroxyapatite (HA) nanoparticle based drug formulation in a rat model of postmenopausal osteoporosis. By a classical adsorption method, nanoparticles of HA loaded with ZOL (HNLZ) drug formulation with a size range of 100-130 nm were prepared. 56 female Wistar rats were ovariectomized (OVX) or sham-operated at 3 months of age. Twelve weeks post surgery, rats were randomized into seven groups and treated with various doses of HNLZ (100, 50 and 25 mu g/kg, intravenous single dose), ZOL (100 mu g/kg, intravenous single dose) and HA nanoparticle (100 mu g/kg, intravenous single dose). Untreated OVX and sham OVX served as controls. After three months treatment period, we evaluated the mechanical properties of the lumbar vertebra and femoral mid-shaft. Femurs were also tested for trabecular microarchitecture. Sensitive biochemical markers of bone formation and bone resorption in serum were also determined. With respect to improvement in the mechanical strength of the lumbar spine and the femoral mid-shaft, the therapy with HNLZ drug formulation was more effective than ZOL therapy in OVX rats. Moreover, HNLZ drug therapy preserved the trabecular microarchitecture better than ZOL therapy in OVX rats. Furthermore, the HNLZ drug formulation corrected increase in serum levels of bone-specific alkaline phosphatase, procollagen type I N-terminal propeptide, osteocalcin, tartrate-resistant acid phosphatase 5b and C-telopeptide of type 1 collagen better than ZOL therapy in OVX rats. The results strongly suggest that HNLZ novel drug formulation appears to be more effective approach for treating severe osteoporosis in humans. (C) 2014 Elsevier B.V. All rights reserved.

Fishery atlas of the Northwestern Hawaiian Islands

This atlas summarizes data on the crustaceans, molluscs, and fishes caught in a resource survey of the Northwestern Hawaiian Islands from October 1976 to September 1981. The geographical and depth distributions, size range, and the type of gear used to catch all of the crustaceans, molluscs, and fishes are tabulated. Species accounts of 37 crustaceans, molluscs, and fishes of commercial potential are presented. The geography, oceanography, and climate of the region are reviewed. (PDF file contains 38 pages.)

Distribution of skipjack in the Pacific Ocean, based on records of incidental catches of the Japanese longline tuna fishery

ENGLISH: All available longline data on skipjack captured in the Pacific Ocean by Japanese research vessels (1949-1965) and from incidental skipjack catches by Japanese commercial vessels (1956-1964) were analyzed. As skipjack are not specifically sought by longline vessels, the data are limited. Considering this it was found that: longline gear captures skipjack of wider size-range and is more selective for larger skipjack than conventional fishing methods, i.e. pole-and-line and purse-seine; skipjack are widely and almost continuously distributed across the Pacific; throughout the year average hook-rates are greater in the southeastern Pacific than in the northwestern Pacific; areas of high hook-rate shift south during the second and third quarters and north during the first and fourth quarters; in the western Pacific the north-south range of the catch distribution was greatest in the first and fourth quarters; skipjack hook-rates are relatively high in the northwestern Pacific east of Japan only during the first and fourth quarters; the highest hook-rates were recorded in extensive areas along the equator (from lO°N to 20°8 between approximately 155°W-100°W); generally more skipjack were captured by research longline gear in water temperature ranges approaching both the upper and lower temperature limits of skipjack distribution (18-21C and 26-28C), than is the case in surface skipjack fisheries; tentative comparisons of longline skipjack catch distributions with Pacific current systems, suggests low skipjack abundance in both North Pacific Central and North Pacific Equatorial water; the sex ratio was 95 males : 63 females in a small sample of skipjack examined; longlines capture skipjack of three, and possibly more, age groups; in skipjack size-composition samples studied, the smaller modal group (65 cm) observed in January-March in the northwestern Pacific (1600E-180oE and 20oN-45°N) corresponds in size to the larger modal group appearing in the late-summer surface fishery off the Izu-Bonin Islands southeast of Japan, and also compares in modal size to the skipjack taken in the Hawaiian fishery in spring time; the analysis of skipjack catches by hook position on the longline and by death-rate studies, indicates that part of the catch is made while the gear is in motion near the surface, and a lesser part of the catch is made when the gear is stabilized at a depth of 70 to 140 m. A brief discussion is given, in the light of new information presented, on several hypotheses by other authors concerning the population structure and migration of skipjack in the Pacific Ocean. SPANISH: Se analizaron todos los datos disponibles de la pesca con palangre de barriletes capturados en el Océano Pacífico por barcos japoneses de investigación (1949-1965) y por las capturas incidentales de los barcos comerciales japoneses (1956-1964). Como los barcos palangreros específicamente, no persiguen al barrilete, los datos son limitados. Considerando ésto, se encontró: que el arte palangrero obtiene barriletes con una distribución más amplia de tallas, y es más selectivo en cuanto a los barriletes de mayor talla, que los métodos convencionales de pesca, Le. cañas de pescar y redes de cerco; el barrilete se encuentra amplia y casi continuamente distribuido a través del Pacífico; en todo el año, las tasas promedio de captura por anzuelo son superiores en el Pacífico sudoriental que las del Pacífico noroeste; las áreas con una tasa alta de captura por anzuelo, se cambian hacia el sur durante los trimestres segundo y tercero, y durante los trimestres primero y cuarto hacia el norte; en el Pacífico occidental la amplitud de la distribución de captura norte-sur, fue superior en los trimestres primero y cuarto; las tasas de captura por anzuelo de barrilete, son relativamente altas en el Pacífico noroeste al este del Japón, únicamente durante los trimestres primero y cuarto; las tasas de captura por anzuelo más altas fueron registradas en extensas áreas a lo largo del ecuador (desde los 10°N hasta los 20°S, aproximadamente entre los 155°W-100°W) ; generalmente las artes palangreras de investigación capturaron más barrilete en aguas en las que la temperatura se aproximaba a los límites más altos o bajos de la temperatura en la distribución del barrilete (18-21 C y 26-28 C), que en el caso de la pesca superficial de barrilete; las comparaciones tentativas de la captura de barrilete con palangre, con el sistema de las corrientes del Pacífico, sugieren una abundancia inferior de barrilete tanto en las aguas del Pacífico central del norte como en las del Pacífico ecuatorial del norte; la proporcíon sexual examinada en una pequeña muestra de barriletes, fue de 95 machos y 63 hembras; los palangreros capturan barriletes de tres grupos de edad y posiblemente de más; en las muestras estudiadas de la composición de las tallas de barrilete, el grupo modal más pequeño (65 cm), observado en enero-marzo en el Pacífico noroeste (160 0E-180° y 20 oN-45°N), corresponde en talla al grupo modal más grande que aparece en la pesca de superficie a fines del verano frente a las Islas Izu-Bonín al sudeste del Japón, y se compara también con la talla modal del barrilete obtenido en la pesca hawaiana en la época de primavera; el análisis de las capturas de barrilete por medio del estudio de la posición de los anzuelos en el palangre y por la tasa de mortalidad, indica que parte de la captura se efectúa cuando el equipo está en movimiento cerca a la superficie y una parte inferior de la captura se realiza, cuando las artes se estabilizan a una profundidad de 70 a 140 m. Se ofrece una breve discusión sobre varias hipótesis de otros autores, en vista de la nueva información presentada referente a la estructura poblacional y a la migración del barrilete en el Océano Pacífico. (PDF contains 100 pages.)

Growth of yellowfin tuna, Thunnus albacares, in the Eastern Pacific Ocean based on otolith increments

ENGLISH: The growth of yellowfin tuna in the eastern Pacific is described in terms of several measurements taken from the fish and their otoliths (sagittae). Equations are also developed to predict age from the readily available dimensions of fork length and head length. The data for all of these relationships were obtained from a sample of 196 fish collected during 1977 through 1979 from purse seiners fishing north of the equator and east of 137°W. The fork-length range of the sample was 30-170 cm. The number of increments on a sagitta of each fish was used as a direct estimate of its age in days. The correspondence between increments and days has been validated for yellowfin in the length range of 40-110 cm. Circumstantial evidence indicates that the relationship also applies in the intervals of 0-40 cm and 110-170 cm. This circumstancial evidence was derived from: 1) literature on validated increments during early growth for other species, 2) knowledge that structures assumed to be daily increments on yellowfin otoliths have subsequently been validated in the corresponding zone on bluefin otoliths, and 3) a comparison of the growth curve based on increments to others obtained from length frequency modal analysis. Based on this information the age estimates over the entire size range of sampled fish are believed to be accurate. In addition to the general growth and age-predictive relationships, the major conclusions of the study are that: 1) Sexually dimorphic growth exists in terms of fork length, fish weight and the length of the otolith counting path for the entire data set. Examination of the data for 1977 and 1979 also revealed that the fork-length growth of each sex differed within years. 2) For combined sexes there were significant differences among the fork-length growth curves for yellowfin sampled in different years. 3) Yellowfin caught inshore (within 275 miles of the coast) were heavier than those caught offshore for fork lengths between 30 and 110 cm. The situation was reversed for lengths greater than 110 cm. 4) Back-calculated spawning months were distributed uniformly throughout the year in 1974 and 1977, but in 1975-1976 and 1978 spawning activity was apparently concentrated in the latter half of the year. SPANISH: El crecimiento del atún aleta amarilla en el Pacífico oriental se describe en términos de varias medidas obtenidas de peces y otolitos (sagita). Se formularon también ecuaciones para pronosticar la edad, según las dimensiones fácilmente disponibles de la longitud horquilla y longitud de la cabeza. Los datos de todas estas relaciones fueron obtenidos mediante una muestra de 196 peces recolectados desde 1977hasta 1979, en barcos cerqueros que estaban pescando al norte de la línea ecuatorial y al este de los 137°W. El intervalo de la longitud horquilla de la muestra fue de 30-170 cm. Se empleó el número de incrementos en la sagita de cada pez como un estimado directo de la edad en días. Se ha comprobado la relación entre los incrementos y los días en el intervalo de longitud de 40-110 cm del aleta amarilla. La evidencia circunstancial indica que se aplica también la relación a los intervalos de 0-40 cm y 110-170 cm. Esta evidencia circunstancial se dedujo: 1) de las publicaciones sobre incrementos comprobados de otras especies durante el primer crecimiento, 2) del conocimientoque las estructuras que se supone son incrementos diarios en los otolitos del aleta amarilla han sido comprobadas luego en la parte correspondiente de otolitos del aleta azul y 3) por una comparación de la curva de crecimiento, basada en incrementos relacionados a otras curvas obtenidas según el análisis modal frecuencia-talla. Se cree, basados en esta información, que las estimaciones de la edad sobre toda la amplitud de talla de los peces muestreados, es acertada. Además de la relación del crecimiento general y del pronóstico de la edad, las principales conclusiones de este estudio son: 1) En toda la serie de datos existe el crecimiento sexualmente dimórfico en términos de longitud horquilla, peso del pez y longitud del plano de conteo del otolito. El examen de los datos de 1977 y 1979, revelan también que el crecimiento longitud horquilla de cada sexo es diferente en los años. 2) En los sexos combinados hubo diferencias significativas entre las curvas de crecimiento longitud horquilla del aleta amarilla muestreado en diferentes años. 3) El aleta amarilla capturado cerca a la costa (en las primeras 275 millas) fue más pesado que el capturado en las aguas mar afuera, correspondiente a la longitud horquilla entre 30 y 110 cm. La situación fue inversa para tallas de más de 110 cm. 4) En 1974 y 1977, los meses retrocalculados del desove se distribuyeron uniformemente durante el año, pero en 1975-1976 y 1978, la actividad del desove se concentró aparentemente en el último semestre del año. (PDF contains 62 pages.)