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At least 19 records

Monodisperse Latex Reactor (MLR): A materials processing space shuttle mid-deck payload

The monodisperse latex reactor experiment has flown five times on the space shuttle, with three more flights currently planned. The objectives of this project is to manufacture, in the microgravity environment of space, large particle-size monodisperse polystyrene latexes in particle sizes larger and more uniform than can be manufactured on Earth. Historically it has been extremely difficult, if not impossible to manufacture in quantity very high quality monodisperse latexes on Earth in particle sizes much above several micrometers in diameter due to buoyancy and sedimentation problems during the polymerization reaction. However the MLR project has succeeded in manufacturing in microgravity monodisperse latex particles as large as 30 micrometers in diameter with a standard deviation of 1.4 percent. It is expected that 100 micrometer particles will have been produced by the completion of the the three remaining flights. These tiny, highly uniform latex microspheres have become the first material to be commercially marketed that was manufactured in space.

Kornfeld, D. M.↗

Large-size monodisperse latexes as a commercial space product

Proposed spacelab production of large-size (2-40 micron diameter) monodispersed latexes is discussed. Explanations are given for the present lack of monodisperse particles in this size range. The four main topics discussed are: (1) the potential uses of these large particle size latexes, (2) why it is necessary for the particles to have a very narrow size distribution, (3) why large amounts of these monodisperse latexes are needed, and (4) why it is necessary to go to microgravity to prepare these latexes.

Kornfeld, D. M.↗

Production of large-particle-size monodisperse latexes

The research program achieved two objectives: (1) it has refined and extended the experimental techniques for preparing monodisperse latexes in quantity on the ground up to a particle diameter of 10 microns; and (2) it has demonstrated that a microgravity environment can be used to grow monodisperse latexes to larger sizes, where the limitations in size have yet to be defined. The experimental development of the monodisperse latex reactor (MLR) and the seeded emulsion polymerizations carried out in the laboratory prototype of the flight hardware, as a function of the operational parameters is discussed. The emphasis is directed towards the measurement, interpretation, and modeling of the kinetics of seeded emulsion polymerization and successive seeded emulsion polymerization. The recipe development of seeded emulsion polymerization as a function of particle size is discussed. The equilibrium swelling of latex particles with monomers was investigated both theoretically and experimentally. Extensive studies are reported on both the type and concentration of initiators, surfactants, and inhibitors, which eventually led to the development of the flight recipes. The experimental results of the flight experiments are discussed, as well as the experimental development of inhibition of seeded emulsion polymerization in terms of time of inhibition and the effect of inhibitors on the kinetics of polymerization.

Vanderhoff, J. W.↗

Kinetics of successive seeding of monodisperse polystyrene latexes. I - Initiation via potassium persulfate. II - Azo initiators with and without inhibitors

The polymerization kinetics of monodisperse polystyrene latexes with diameters of 1 micron are studied. The monodisperse latexes were prepared by the successive seeding method using 1 mM K2S2O8 with an 8 percent emulsifier surface coverage and 0.5 mM K2S2O8 with a 4 percent emulsifier surface coverage, and the kinetics were measured in a piston/cylinder dialometer. The data reveal that the polymerization rate decreases with increasing particle size; and the surface charge decreases with increasing particle size. The effects of initiators (AIBN and AMBN) and inhibitors (NH24SCN, NaNO2, and hydroquinone) on the product monodispersity and polymerization kinetics of latexes with diameters greater than 1 micron are investigated in a second experiment. It is observed that hydroquinone combined with AMBN are most effective in reducing nucleation without causing flocculation. It is noted that the kinetic transition from emulsion to bulk is complete for a particle size exceeding 1 micron in which the polymerization rate is independent of the particle size.

Sudol, E. D.↗

Generation of monodisperse droplets by spontaneous condensation of flow in nozzles

Submicron size monodisperse particles are of interest in many industrial and scientific applications. These include the manufacture of ceramic parts using fine ceramic particles, the production of thin films by deposition of ionized clusters, monodisperse seed particles for laser anemometry, and the study of size dependence of cluster chemical and physical properties. An inexpensive and relatively easy way to generate such particles is by utilizing the phenomenon of spontaneous condensation. The phenomenon occurs when the vapor or a mixture of a vapor and a noncondensing gas is expanded at a high expansion rate. The saturation line is crossed with the supercooled vapor behaving like a gas, until all of a sudden at the so called Wilson point, condensation occurs, resulting in a large number of relatively monodisperse droplets. The droplet size is a function of the expansion rate, inlet conditions, mass fraction of vapor, gas properties, etc. Spontaneous condensation of steam and water vapor and air mixture in a one dimensional nozzle was modeled and the resulting equations solved numerically. The droplet size distribution at the exit of various one dimensional nozzles and the flow characteristics such as pressure ratio, mean droplet radius, vapor and droplet temperatures, nucleation flux, supercooling, wetness, etc., along the axial distance were obtained. The numerical results compared very well with the available experimental data. The effect of inlet conditions, nozzle expansion rates, and vapor mass fractions on droplet mean radius, droplet size distribution, and pressure ratio were examined.

Lai, Der-Shaiun↗

Synthesis and Self-Assembly of Monodisperse Graphene Nanoribbons: Access to Submicron Architectures with Long-Range Order and Uniform Orientation

Fabricating organic semiconducting materials into large-scale well-organized architectures is critical for building high performance molecular electronics. While graphene nanoribbons (GNRs) hold enormous promise for various device applications, their assembly into a well-structured monolayer or multilayer architecture poses a substantial challenge. Here we report the preparation of length-defined monodisperse GNRs via the integrated iterative binomial synthesis (IIBS) strategy and their self-assembly into submicron-architectures with long-range order, uniform orientation as well as regular layers. Further, the use of short alkyl side chains benefits forming stable multi-layers through interlocking structures. By changing the length and backbone shapes of these monodisperse GNRs, various three-dimensional assemblies including multilayer stripes, monolayer stripes, and nanowires, can be achieved, leading to different photophysical properties and band gaps. The discovery of these intriguing self-assembly behaviors of length-defined GNRs is expected to open the door for various future applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of monodisperse high entropy alloy nanocatalysts from core@shell nanoparticles

We report that high-entropy alloy (HEA) nanoparticles (NPs) hold great promise in electrocatalysis because of their nearly unlimited compositions, tailorable active sites, and high durability. However, the synthesis of these compositionally complex structures as monodisperse NPs remains a challenge by colloidal routes because the different rates of metal precursor reduction lead to phase separation. Here, we report the conversion of core@shell NPs into HEA NPs through annealing, with conservation of sample monodispersity. This potentially general route for high-quality HEA NPs was demonstrated by preparing PdCu@PtNiCo NPs via seed-mediated co-reduction, wherein Pt, Ni, and Co were co-deposited on PdCu seeds in solution. These multimetallic NPs were then converted to single-crystalline and single-phase PdCuPtNiCo NPs through annealing. On account of their small particle size, highly dispersed Pt/Pd content, and low elemental diffusivity, these HEA NPs were found to be a highly efficient and durable catalyst for the oxygen reduction reaction. They were also highly selective for the four-electron transfer pathway. We expect that this new synthetic strategy will facilitate the synthesis of new HEA NPs for catalysis and other applications.

36 MATERIALS SCIENCE↗

Understanding palladium–tellurium cluster formation on WTe2: From a kinetically hindered distribution to thermodynamically controlled monodispersity

Abstract A fundamental understanding of the transition metal dichalcogenide (TMDC)–metal interface is critical for their utilization in a broad range of applications. We investigate how the deposition of palladium (Pd), as a model metal, on WTe2(001), leads to the assembly of Pd into clusters and nanoparticles. Using X-ray photoemission spectroscopy, scanning tunneling microscopy imaging, and ab initio simulations, we find that Pd nucleation is driven by the interaction with and the availability of mobile excess tellurium (Te) leading to the formation of Pd-Te clusters at room temperature. Surprisingly, the nucleation of Pd-Te clusters is not affected by intrinsic surface defects, even at elevated temperatures. Upon annealing, the Pd-Te nanoclusters adopt an identical nanostructure and are stable up to ∼523 K. Density functional theory calculations provide a foundation for our understanding of the mobility of Pd and Te atoms, preferential nucleation of Pd-Te clusters, and the origin of their annealing-induced monodispersity. These results highlight the role the excess chalcogenide atoms may play in the metal deposition process. More broadly, the discoveries of synthetic pathways yielding thermally robust monodispersed nanostructures on TMDCs are critical to the manufacturing of novel quantum and microelectronics devices and catalytically active nano-alloy centers.

36 MATERIALS SCIENCE↗

Electrochemical Synthesis of Monodisperse Platinum-Cobalt Nanocrystals

The synthesis of platinum-cobalt nanocrystals (NCs) using colloidal solvothermal techniques is well understood. However, for monodisperse NCs to form, high temperatures and environmentally detrimental solvents are needed. We report a room temperature, aqueous method of platinum-cobalt NC synthesis using electrochemical reduction as the driving force for nucleation and growth. It is found that colloidal NCs will form in both the presence and absence of surfactant. Additionally, we report a monodisperse electrochemical deposition of NCs utilising a transparent conducting oxide electrode. The methods developed here will allow for a synthetic method to produce nanocatalysts with minimal environmental impact and should be readily applicable to other NC systems, including single- and multi-component alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monodisperse atomizers for agricultural aviation applications

Conceptual designs of two monodisperse spray nozzles are described and the rationale used in each design is discussed. The nozzles were designed to eliminate present problems in agricultural aviation applications, such as ineffective plant coverage, drift due to small droplets present in the spray being dispersed, and nonuniform swath coverages. Monodisperse atomization techniques are reviewed and a synopsis of the information obtained concerning agricultural aviation spray applications is presented.

Christensen, L. S.↗

Viscoelastic properties of entangled polymers - Ternary blends of monodisperse homopolymers

In a previous publication from this laboratory, the Rouse-Bueche-Zimm molecular theory of viscoelasticity has been extended by using a transient network model to apply to binary blends of monodisperse polymers with chain entanglements. The dynamics of the entanglements were modeled both by the enhanced frictional coefficients and by the additional elastic couplings. It was recognized that entanglements not only may form between chains of the same lengths (intracomponent entanglements) but also between those of different lengths (intercomponent entanglements). At a given intercomponent entanglement, the longer chain was assumed to have the frictional coefficient of the shorter chain. Similarly, for blends consisting of several monodisperse components with different molecular weights, such modifications are also required to predict their linear viscoelastic behavior. The frequency of these interactions is assumed to be proportional to the weight ratio of the respective component chains in the blend. Equations of motion are formulated for each component and solved numerically for the relaxation time spectra. Linear viscoelastic properties such as the dynamic mechanical moduli, stress relaxation moduli, and zero-shear viscosity can then be computed for these systems by linear summation of those of the components.

Soong, D.↗

Process for preparation of large-particle-size monodisperse latexes

Monodisperse latexes having a particle size in the range of 2 to 40 microns are prepared by seeded emulsion polymerization in microgravity. A reaction mixture containing smaller monodisperse latex seed particles, predetermined amounts of monomer, emulsifier, initiator, inhibitor and water is placed in a microgravity environment, and polymerization is initiated by heating. The reaction is allowed to continue until the seed particles grow to a predetermined size, and the resulting enlarged particles are then recovered. A plurality of particle-growing steps can be used to reach larger sizes within the stated range, with enlarge particles from the previous steps being used as seed particles for the succeeding steps. Microgravity enables preparation of particles in the stated size range by avoiding gravity related problems of creaming and settling, and flocculation induced by mechanical shear that have precluded their preparation in a normal gravity environment.

Vanderhoff, J. W.↗

Formation of oxides of nitrogen in monodisperse spray combustion of hydrocarbon fuels

Experimental results of exit plane NO/NO(x) emissions from atmospheric monodisperse fuel spray combustion are presented. Six different hydrocarbon fuels were studied: isopropanol, n-propanol, n-octane, iso-octane, n-heptane and methanol. The results indicate an optimum droplet size for minimizing NO/NO(x) production for all of the test fuels. At the optimum droplet diameter, reductions in NO/NO(x) relative to the NO(x) occurred at droplet diameters of 55 and 48 microns respectively, as compared to a 50-micron droplet size for isopropanol. The occurrence of the minimum NO(x) point at different droplet diameters for the different fuels appears to be governed by the extent of prevaporization of the fuel in the spray, and is consistent with theoretical calculations based on each fuel's physical properties. Estimates are also given for the behavior of heavy fuels and of polydisperse fuel sprays in shifting the minimum NO(x) point compared to a monodisperse situation.

Nizami, A. A.↗

Pollutant Formation in Monodisperse Fuel Spray Combustion

The combustion of liquid sprays represents an extremely important class of combustion processes. In the transition region, encompassing droplet sizes in the range of 25-80 micron diameter, the mixing and evaporation processes are both incomplete at the flame front and burning occurs in a combined diffusive and premixed fashion. Under these conditions, the relative importance of heterogeneous and homogeneous effects in dominating the combustion process is switched and gives rise to a number of interesting phenomena. NO (sub x) formation in monodisperse spray combustion was investigated with the following specific objectives: (1) to quantitatively determine the effect of droplet size, number density, etc. on NO sub x formation in monodisperse fuel spray combustion; and (2) to isolate the important physical and chemical phenomena in NO sub x formation in these combustion systems.

Cernansky, N. P.↗

Preparation of large-particle-size monodisperse latexes in space: The STS-3, STS-4, and STS-7 mission results

Large-particle-size monodisperse latexes were prepared on four STS missions of the space shuttles Columbia and Challenger using flight hardware comprising four automated 100 cm(3) polymerization reactors. Seven polymerizations carried out on the March 1982 STS-3 mission of the Columbia, and the April 1983 STS-6 and June 1983 STS-7 missions of the Challenger, gave monodisperse latexes of 5 to 18 micron diameter with narrower particle size distributions than the corresponding ground-based control polymerizations. The rates of polymerization in microgravity were the same as on Earth. The results of these experiments are reviewed, and the prospects of the development of a space production process are discussed.

Vanderhoff, J. W.↗

Production of Large-Particle-Size Monodisperse Latexes in Microgravity

A latex is a suspension of very tiny (micrometer-size) plastic spheres in water, stabilized by emulsifiers. The growth of billions of these tiny plastic spheres to sizes larger than can be grown on Earth is attempted while keeping all of them exactly the same size and perfectly spherical. Thus far on several of the Monodisperse Latex Reactor (MLR) flights, the latex spheres have been returned to Earth with standard deviations of better than 1.4%. In microgravity the absence of buoyancy effects has allowed growth of the balls up to 30 micrometers in diameter thus far. The MLR has now flown 5 times on the Shuttle. The MLR has now produced the first commercial space product; that is the first commercial material ever manufactured in space and marketed on Earth. Once it is demonstrated that these large-size-monodisperse latexes can be routinely produced in quantity and quality, they can be marketed for many types of scientific applications. They can be used in biomedical research for such things as drug carriers and tracers in the body, human and animal blood flow studies, membrane and pore-sizing in the body, and medical diagnostic tests.

Vanderhoff, J. W.↗

Representation of the vaporization behavior of turbulent polydisperse sprays by equivalent monodisperse sprays

The concept of using an equivalent monodisperse spray to represent the vaporization behavior of polydisperse sprays has been examined by numerically solving two turbulent vaporizing sprays. One involves the injection of Freon-11 in a still environment, whereas the other is a methanol spray in a still but hot environment. The use of three different mean sizes, namely, Sauter mean diameter, volume median diameter, and surface-area mean diameter, has been investigated. Results indicate a good degree of correlation between the polydisperse spray and its equivalent monodisperse sprays represented by the volume median diameter and the Sauter mean diameter, the former giving slightly better results. The surface-area mean diameter does not provide as good a correlation as the other two mean diameters.

Aggarwal, S. K.↗

The first products made in space - Monodisperse latex particles

Monodisperse latex particles developed by seeded emulsion polymerization on various Space Shuttle flights are analyzed. The flight hardware was composed of a monodisperse latex reactor and a support electronics package, and the particles were examined by optical microscopy and TEM. Data on the particle size distributions, larger and smaller off-size particles, and conversion-time curves for the particles are examined and compared to ground-based results. It is observed that the ground-based polymerizations have more coagulum than the flight polymerizations; the flight latex particles have narrower size distributions than the ground particles; and the number of off-size larger particles in the flight particles is smaller than in the ground data.

Vanderhoff, J. W.↗