Water Vapor Barrier Material by Covalent Self-Assembly for Organic Device Encapsulation

Development of barrier materials for organic device encapsulation is of key interest for the commercialization of organic electronics. In this work, we have fabricated barrier films with ultralow water vapor permeabilities by reactive layer-by-layer approach. Using this technique, alternative layers of polyethylene imine and stearic acid were covalently bonded on a Surlyn film. The roughness, transparency and thickness of the films were determined by atomic force microscopy, UV-visible spectroscopy and scanning electron microscopy, respectively. Water vapor transmission rates through these films and the ability of these films to protect the organic photovoltaic devices was investigated. The films with covalently assembled bilayers exhibited lower water vapor transmission rates and maintained higher organic photovoltaic device efficiencies compared to the neat Surlyn film.

A Surlyn/magnesium oxide nanocomposite as an effective water vapor barrier for organic device encapsulation

A reactive polymer nanocomposite system was proposed as an effective water vapor barrier material for organic device encapsulation. Nanosized magnesium oxide (MgO) was synthesized by the solution combustion technique using two different fuels, lactose and alanine. The purity and crystallite size of MgO were determined from X-ray diffraction studies. The surface areas and porosity measurements were used to determine the water adsorption capacities of MgO. Nanocomposites with various concentrations (wt% = 0.25, 0.5, 1 and 2.5) of MgO were prepared using Surlyn as the base polymer. The permeation rate of moisture through the fabricated films was calculated using calcium degradation test and these rates were further used to calculate the diffusivities. Accelerated aging experiments were conducted to study the performance of organic photovoltaic devices encapsulated with synthesized films under accelerated weathering conditions. The performance of the barrier materials with synthesized MgO was also compared to that obtained with commercial MgO. The films containing MgO obtained from lactose exhibited better barrier properties compared to other films made with commercial MgO and MgO synthesized using alanine as well as other nanocomposites reported in the literature.

Reactive interlayer based ultra-low moisture permeable membranes for organic photovoltaic encapsulation

Reactive interlayers consisting of zero valent iron and copper nanoparticles have been successfully incorporated into Surlyn films to fabricate moisture barrier materials with reduced water vapor permeabilities. The reactive nanoparticles dispersed in stearic acid were employed as the interlayers due to their ability to react with moisture. The water vapor transmission rates through the fabricated barrier films with reactive iron and copper interlayers decreased by over 4 orders of magnitude when compared to neat Surlyn. The flexibility and transparency of the barrier films have been evaluated by tensile and UV-visible experiments. Moreover, the accelerated aging studies conducted in accordance with the ISOS-III protocol confirmed the increased lifetimes of the organic photovoltaic (OPV) devices encapsulated with these reactive barrier films.

Ultra-small sulphur nanoparticles configured inside a flexible organic mixed conducting network as a cathode for lithium-sulphur batteries

The major challenges in Li-S batteries are the formation of soluble polysulphides during the reversible conversion of S-8 <-> Li2S, large changes in sulphur particle volume during lithiation and extremely poor charge transport in sulphur. We demonstrate here a novel and simple strategy to overcome these challenges towards practical realization of a stable high performance Li-S battery. For the first time, a strategy is developed which does away with the necessity of pre-fabricated high surface area hollow-structured adsorbates and also multiple nontrivial synthesis steps related to sulphur loading inside such adsorbates. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li-S batteries. The PEG and PAni network around the sulphur nanoparticles serves as an efficient flexible trap for sulphur and polysulphides and also provides distinct pathways for electrons (through PAni) and ions (through PEG) during battery operation. Contrary to the cathodes demonstrated based on various carbon-sulphur composites, the mixed conducting S-MIEC showed an extremely high loading of 75%. The S-MIEC exhibited a stable capacity of nearly 900 mA h g(-1) at the end of 100 cycles at a 1C current rate.

Organic fluorine involved intramolecular hydrogen bonds in the derivatives of imides: NMR evidence corroborated by DFT based theoretical calculations

The rare occurrence of intramolecular hydrogen bonds (HBs) of the type N-H center dot center dot center dot F-C is detected in the derivatives of imides in a low polarity solvent by using multi-dimensional and multinuclear NMR experiments. The observation of (1h)J(FH), (2h)J(FN), and (2h)J(FF), where the spin magnetization is transmitted through space among the interacting NMR active nuclei, provided strong and unambiguous evidence for the existence of intra-molecular HBs. The variation in the chemical shifts of labile protons depending on physical conditions, such as the solvent dilution and the systematic alteration of temperature confirmed the presence of weak interactions through intramolecular HBs in all the investigated fluorine substituted molecules. The self or cross dimerization of molecules is unequivocally discarded by the analysis of the rates of diffusion obtained using pseudo-two dimensional DOSY experiments. The Density Function Theory (DFT) calculations based on the Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings.

High Loading of Pd Nanoparticles by Interior Functionalization of MOFs for Heterogeneous Catalysis

In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd2+ (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs. The loading amount of Pd NPs was increased monotonically without altering their size distribution on a particular MOF. Importantly, the distinct role of alkyne groups for Pe(2+) stabilization has also been demonstrated by performing a control experiment considering a MOF without an alkyne moiety. The preparation of NPs involved two distinct steps viz. adsorption of metal ions inside MOFs and reduction of metal ions. Both of these steps were monitored by microscopic techniques. This report also demonstrates the applicability of Pd@MOF NPs as extremely efficient heterogeneous catalysts for Heck-coupling and hydrogenation reactions of aryl bromides or iodides and alkenes, respectively.

Microstructure and mechanical behaviour of a SiC particles reinforced Al-5Cu composite under dynamic loading

The mechanical behaviour of a composite of Al–5Cu matrix reinforced with 15% SiC particles was studied at different strain rates from 1×10−3 to 2.5×103 s−1 using both a conventional universal testing machine (for low strain-rate tests) and a split Hopkinson bar (for tests at dynamic strain rates). Whilst the yield stress of the composite increases as the strain rate increases, the maximum flow stresses, 440 MPa for compression and 450 MPa for tension, are independent of strain rate. The microstructures and defect structures of the deformed composite were studied with both scanning electron microscopy and transmission electron microscopy and were correlated to the observed mechanical behaviour. Fracture surface studies of samples after dynamic tensile testing indicates that failure of the composite is controlled by ductile failure of the aluminium matrix by the nucleation, growth and coalescence of voids.

Quantifying the Effects of Contact Duration, Loading Rate, and Approach Velocity on P-Selectin-PSGL-1 Interactions Using AFM

Kinetics and its regulation by extrinsic physical factors govern selectin-ligand interactions that mediate tethering and rolling of circulating cells on the vessel wall under hemodynamic forces. While the force regulation of off-rate for dissociation of selectin-ligand bonds has been extensively studied, much less is known about how transport impacts the on-rate for association of these bonds and their stability. We used atomic force microscopy (AFM) to quantify how the contact duration, loading rate, and approach velocity affected kinetic rates and strength of bonds of P-selectin interacting with P-selectin glycoprotein ligand I (PSGL-1). We found a saturable relationship between the contact time and the rupture force, a biphasic relationship between the adhesion probability and the retraction velocity, a piece-wise linear relationship between the rupture force and the logarithm of the loading rate, and a threshold relationship between the approach velocity and the rupture force. These results provide new insights into how physical factors regulate receptor-ligand interactions.

Evaluating approaches and technologies for monitoring organic contaminants in the aquatic environment, Ann Arbor, MI, July 21-23, 2006: workshop proceedings

The Alliance for Coastal Technologies (ACT) convened a workshop on Evaluating Approaches and Technologies for Monitoring Organic Contaminants in the Aquatic Environment in Ann Arbor, MI on July 21-23, 2006. The primary objectives of this workshop were to: 1) identify the priority management information needs relative to organic contaminant loading; 2) explore the most appropriate approaches to estimating mass loading; and 3) evaluate the current status of the sensor technology. To meet these objectives, a mixture of leading research scientists, resource managers, and industry representatives were brought together for a focused two-day workshop. The workshop featured four plenary talks followed by breakout sessions in which arranged groups of participants where charged to respond to a series of focused discussion questions. At present, there are major concerns about the inadequacies in approaches and technologies for quantifying mass emissions and detection of organic contaminants for protecting municipal water supplies and receiving waters. Managers use estimates of land-based contaminant loadings to rivers, lakes, and oceans to assess relative risk among various contaminant sources, determine compliance with regulatory standards, and define progress in source reduction. However, accurately quantifying contaminant loading remains a major challenge. Loading occurs over a range of hydrologic conditions, requiring measurement technologies that can accommodate a broad range of ambient conditions. In addition, in situ chemical sensors that provide a means for acquiring continuous concentration measurements are still under development, particularly for organic contaminants that typically occur at low concentrations. Better approaches and strategies for estimating contaminant loading, including evaluations of both sampling design and sensor technologies, need to be identified. The following general recommendations were made in an effort to advance future organic contaminant monitoring: 1. Improve the understanding of material balance in aquatic systems and the relationship between potential surrogate measures (e.g., DOC, chlorophyll, particle size distribution) and target constituents. 2. Develop continuous real-time sensors to be used by managers as screening measures and triggers for more intensive monitoring. 3. Pursue surrogate measures and indicators of organic pollutant contamination, such as CDOM, turbidity, or non-equilibrium partitioning. 4. Develop continuous field-deployable sensors for PCBs, PAHs, pyrethroids, and emerging contaminants of concern and develop strategies that couple sampling approaches with tools that incorporate sensor synergy (i.e., measure appropriate surrogates along with the dissolved organics to allow full mass emission estimation).[PDF contains 20 pages]

Organic pollution in culture water resulting from excess feed and metabolite buildup

Penaeus monodon postlarvae were subjected to increasing feed concentrations and their growth and survival rates were recorded. Measurements were made of dissolved organic matter, and ammonia and nitrite-nitrogen concentrations. Survival was highest at the lowest feeding level and decreased as feed concentration increased. It is concluded that although organic matter enriches the food supply for P. monodon postlarvae, at higher concentration levels it can pollute the culture water, which in turn leads to mass mortality of the postlarvae. Secondly, the survival rate of P. monodon postlarvae is directly related to dissolved organic matter concentration, oxygen tension, and ammonia-nitrogen concentrations in the culture water. Even at sublethal levels these adverse environmental conditions decrease the survival rate.

Blade Loading and Its Application in the Mean-Line Design of Low Pressure Turbines

In order to minimize the number of iterations to a turbine design, reasonable choices of the key parameters must be made at the preliminary design stage. The choice of blade loading is of particular concern in the low pressure (LP) turbine of civil aero engines, where the use of high-lift blades is widespread. This paper considers how blade loading should be measured, compares the performance of various loss correlations, and explores the impact of blade lift on performance and lapse rates. To these ends, an analytical design study is presented for a repeating-stage, axial-flow LP turbine. It is demonstrated that the long-established Zweifel lift coefficient (Zweifel, 1945, "The Spacing of Turbomachine Blading, Especially with Large Angular Deflection" Brown Boveri Rev., 32(1), pp. 436-444) is flawed because it does not account for the blade camber. As a result the Zweifel coefficient is only meaningful for a fixed set of flow angles and cannot be used as an absolute measure of blade loading. A lift coefficient based on circulation is instead proposed that accounts for the blade curvature and is independent of the flow angles. Various existing profile and secondary loss correlations are examined for their suitability to preliminary design. A largely qualitative comparison demonstrates that the loss correlations based on Ainley and Mathieson (Ainley and Mathieson, 1957, "A Method of Performance Estimation for Axial-Flow Turbines," ARC Reports and Memoranda No. 2974; Dunham and Came, 1970, "Improvements to the Ainley-Mathieson Method of Turbine Performance Prediction," Trans. ASME: J. Eng. Gas Turbines Power, July, pp. 252-256; Kacker and Okapuu, 1982, "A Mean Line Performance Method for Axial Flow Turbine Efficiency," J. Eng. Power, 104, pp. 111-119). are not realistic, while the profile loss model of Coull and Hodson (Coull and Hodson, 2011, "Predicting the Profile Loss of High-Lift Low Pressure Turbines," J. Turbomach., 134(2), pp. 021002) and the secondary loss model of (Traupel, W, 1977, Thermische Turbomaschinen, Springer-Verlag, Berlin) are arguably the most reasonable. A quantitative comparison with multistage rig data indicates that, together, these methods over-predict lapse rates by around 30%, highlighting the need for improved loss models and a better understanding of the multistage environment. By examining the influence of blade lift across the Smith efficiency chart, the analysis demonstrates that designs with higher flow turning will tend to be less sensitive to increases in blade loading. © 2013 American Society of Mechanical Engineers.

Effects of Organic-Rich Sediment and Below-Ground Sulfide Exposure on Submerged Macrophyte, Hydrilla verticillata

The effects of organic-rich sediment and sulfide exposure on Hydrilla verticillata were investigated. The organic richness of sediment was simulated by adding sucrose into sediments, and sulfide exposure was conducted by adding sodium sulfide to plant roots. The length, biomass and density of shoot reduced in the sucrose-amended sediments, and the largest reduction occurred in the highest 1.0% addition treatment by 84.2%, 56.7% and 92.4%, respectively. However, the 0.1% addition treatment stimulated the growth of root. The effects of below-ground sulfide exposure on the physiological activities of H. verticillata were determined by adding sulfide to the below-ground tissue. Significantly inhibitory effects of sulfide were observed on plant photosynthesis, root carbohydrate and nitrogen synthetic reserves. The net photosynthetic rates, soluble carbohydrate and soluble protein contents in root were reduced by 104%, 71.8% and 49.8%, respectively, in the 0.6 mM sulfide treatment.

Contributions of phosphatase and microbial activity to internal phosphorus loading and their relation to lake eutrophication

Phosphatase may accelerate the process of lake eutrophication through improving phosphorus bioavailability. This mechanism was studied in three Chinese eutrophic shallow lakes (Lake Taihu, Lake Longyang,and Lake Lianhua). Phosphatase activity was related to the concentration of soluble reactive phosphorus (SRP) and chlorophyll a. Stability of dissolved phosphatase in reverse micelles may be attributed to molecular size, conformation and active residues of the enzyme. At the site with Microcystis bloomed in Lake Taihu, dissolved phosphatase activity was higher and more stable in micelles, SRP concentrations were lower in interstitial water, the contents of different forms of phosphorus and the amounts of aerobic bacteria were lower while respiration efficiency was higher in sediments. Phosphobacteria, both inorganic and organic and other microorganisms were abundant in surface water but rare in sediments. Therefore, internal phosphorus may substantially flux into water column by enzymatic hydrolysis and anaerobic release, together with mobility of bacteria, thereby initiating the bloom. In short, biological mechanism may act in concert with physical and chemical factors to drive the internal phosphorus release and accelerate lake eutrophication.

Modeling the effect of ozone loss on photobleaching of chromophoric dissolved organic matter in the St. Lawrence estuary

Temporal trends in total ozone for the St. Lawrence estuary were estimated from ground-based measurements at the NOAA/CMDL station in Caribou, Maine. Linear regression analysis showed that from 1979 to 1999 total ozone has decreased by about 3.3% per decade on an annual basis and ≤6.2% per decade on a monthly basis relative to unperturbed (pre-CFC) levels. The influence of increased ultraviolet-B (280–320 nm) radiation associated with ozone depletion on water column photochemical processes was evaluated by modeling the photobleaching of chromophoric dissolved organic material (CDOM). Linear regression analysis showed small (<0.5% per decade), but statistically significant upward trends in maximum noontime photobleaching rates. Most notably, positive trends in relative rates for May, June, and July, when maximum absolute rates are expected, were predicted. A global model based on TOMS ozone data revealed increases in photobleaching of ≤3% per decade at high latitudes in the Southern Hemisphere. Radiation amplification factors for increases in photochemically weighted UV (280–400 nm) in response to ozone depletion were estimated at 0.1 and 0.08 for photobleaching of CDOM absorbance at 300 and 350 nm, respectively. Application of the laboratory-based model to conditions that more closely resembled those in situ were variable with both overestimation and underestimation of measured rates. The differences between modeled rates and observed rates under quasi-natural conditions were as large or larger than the predicted increases due to ozone depletion. These comparisons suggest that biological activity and mixing play an important, but as yet ill-defined, role in modifying photochemical processes.

Novel acidic porous clay heterostructure with highly ordered organic-inorganic hybrid structure: one-pot synthesis of mesoporous organosilica in the galleries of clay

A new class of organic-inorganic hybrid porous clay heterostructures (HPCHs) have been prepared through the surfactant-directed assembly of organosilica in the galleries of montmorillonite. The reaction involved hydrolysis and condensation of phenyltriethoxysilane and tetraethoxysilane in the presence of intragallery surfactant templates (dodecylame and cetyltrimethylammonium ion). The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), N-2 adsorption, solid-state Si-29 and C-13 NMR, and FTIR. XRD patterns indicated a regular interstratification of the clay layers for HPCHs. Depending on loading of phenyl groups, HPCHs had BET surface areas of 390-771 m(2) g(-1), pore volumes of 0.3-0.59 cm(3) g(-1), and the framework pore sizes in the supermicropore to small mesopore range (1.2-2.6 nm). HPCHs were hydrophobic and acidic.