The ozone transfer between atmosphere and vegetation. A study on Scots pine in the field

Ozone (O3) is a reactive gas present in the troposphere in the range of parts per billion (ppb), i.e. molecules of O3 in 109 molecules of air. Its strong oxidative capacity makes it a key element in tropospheric chemistry and a threat to the integrity of materials, including living organisms. Knowledge and control of O3 levels are an issue in relation to indoor air quality, building material endurance, respiratory human disorders, and plant performance. Ozone is also a greenhouse gas and its abundance is relevant to global warming. The interaction of the lower troposphere with vegetated landscapes results in O3 being removed from the atmosphere by reactions that lead to the oxidation of plant-related components. Details on the rate and pattern of removal on different landscapes as well as the ultimate mechanisms by which this occurs are not fully resolved. This thesis analysed the controlling processes of the transfer of ozone at the air-plant interface. Improvement in the knowledge of these processes benefits the prediction of both atmospheric removal of O3 and its impact on vegetation. This study was based on the measurement and analysis of multi-year field measurements of O3 flux to Scots pine (Pinus sylvestris L.) foliage with a shoot-scale gas-exchange enclosure system. In addition, the analyses made use of simultaneous CO2 and H2O exchange, canopy-scale O3, CO2 and H2O exchange, foliage surface wetness, and environmental variables. All data was gathered at the SMEAR measuring station (southern Finland). Enclosure gas-exchange techniques such as those commonly used for the measure of CO2 and water vapour can be applied to the measure of ozone gas-exchange in the field. Through analysis of the system dynamics the occurring disturbances and noise can be identified. In the system used in this study, the possible artefacts arising from the ozone reactivity towards the system materials in combination with low background concentrations need to be taken into account. The main artefact was the loss of ozone towards the chamber walls, which was found to be very variable. The level of wall-loss was obtained from simultaneous and continuous measurements, and was included in the formulation of the mass balance of O3 concentration inside the chamber. The analysis of the field measurements in this study show that the flux of ozone to the Scots pine foliage is generated in about equal proportions by stomatal and non-stomatal controlled processes. Deposition towards foliage and forest is sustained also during night and winter when stomatal gas-exchange is low or absent. The non-stomatal portion of the flux was analysed further. The pattern of flux in time was found to be an overlap of the patterns of biological activity and presence of wetness in the environment. This was seen to occur both at the shoot and canopy scale. The presence of wetness enhanced the flux not only in the presence of liquid droplets but also during existence of a moisture film on the plant surfaces. The existence of these films and their relation to the ozone sinks was determined by simultaneous measurements of leaf surface wetness and ozone flux. The results seem to suggest ozone would be reacting at the foliage surface and the reaction rate would be mediated by the presence of surface wetness. Alternative mechanisms were discussed, including nocturnal stomatal aperture and emission of reactive volatile compounds. The prediction of the total flux could thus be based on a combination of a model of stomatal behaviour and a model of water absorption on the foliage surfaces. The concepts behind the division of stomatal and non-stomatal sinks were reconsidered. This study showed that it is theoretically possible that a sink located before or near the stomatal aperture prevents or diminishes the diffusion of ozone towards the intercellular air space of the mesophyll. This obstacle to stomatal diffusion happens only under certain conditions, which include a very low presence of reaction sites in the mesophyll, an extremely strong sink located on the outer surfaces or stomatal pore. The relevance, or existence, of this process in natural conditions would need to be assessed further. Potentially strong reactions were considered, including dissolved sulphate, volatile organic compounds, and apoplastic ascorbic acid. Information on the location and the relative abundance of these compounds would be valuable. The highest total flux towards the foliage and forest happens when both the plant activity and ambient moisture are high. The highest uptake into the interior of the foliage happens at large stomatal apertures, provided that scavenging reactions located near the stomatal pore are weak or non-existent. The discussion covers the methodological developments of this study, the relevance of the different controlling factors of ozone flux, the partition amongst its component, and the possible mechanisms of non-stomatal uptake.

Effect of plant trichomes on the vertical migration of Haemonchus contortus infective larvae on five tropical forages

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Moisture Effects on the Reliability of Anisotropic Conductive Film Interconnection for Flip Chip on Flex Applications

Anisotropic conductive film (ACF) which consists of an adhesive epoxy matrix and randomly distributed conductive particles are widely used as the connection material for electronic devices with high I/O counts. However, for the semiconductor industry the reliability of the ACF is still a major concern due to a lack of experimental reliability data. This paper reports the investigations into the moisture-induced failures in Flip-Chip-on-Flex interconnections with Anisotropic Conductive Films (ACFs). Both experimental and modeling methods were applied. In the experiments, the contact resistance was used as a quality indicator and was measured continuously during the accelerated tests (autoclave tests). The temperature, relative humidity and the pressure were set at 121°C, 100%RH, and 2atm respectively. The contact resistance of the ACF joints increased during the tests and nearly 25% of the joints were found to be open after 168 hours’ testing time. Visible conduction gaps between the adhesive and substrate pads were observed. Cracks at the adhesive/flex interface were also found. For a better understanding of the experimental results, 3-D Finite Element (FE) models were built and a macro-micro modeling method was used to determine the moisture diffusion and moisture-induced stresses inside the ACF joints. Modeling results are consistent with the findings in the experimental work.

Experimental and Modelling Analysis on the Moisture Induced Failures in Flip Chip on Flex Interconnections with Anisotropic Conductive Film

This paper reports the investigations into the moisture induced failures in flip-chip-on-flex interconnections with anisotropic conductive films (ACF). Both experimental and modeling methods were applied. In the experiments, the contact resistance was used as a quality indicator and was measured continuously during the accelerated tests (autoclave tests). The temperature, relative humidity and the pressure were set at 121°C, 100%RH, 1atm respectively. The contact resistance of the ACF joints increased during the tests and nearly 25% of the joints were found to be open after 168 hours' testing time. Visible conduction gaps between the adhesive and substrate pads were observed. Cracks at the adhesive/flex interface were also found. It is believed that the swelling effect of the adhesive and the water penetration along the adhesive/flex interface are the main causes of this contact degradation. Another finding from the experimental work was that the ACF interconnections that had undergone the reflow treatment were more sensitive to the moisture and showed worse reliability during the tests. For a better understanding of the experimental results, 3D finite element (FE) models were built and a macro-micro modeling method was used to determine the moisture diffusion and moisture-induced stresses inside the ACF joints. Modeling results are consistent with the findings in the experimental work.

Disclosures on a precipitation indicator, moisture detector, vacuum ball valve, film strip printer, normal incidence interferometer, color sorter, and coaxial T. /

Mode of access: Internet.

Moisture uptake and tensile properties of starch-sugar cane fibre films

THERE is an increasing need for biodegradable plastics because they are environmentally friendly and can replace petroleum-based non-degradable plastics which pollute the environment. Starch-derived films reinforced with sugar cane bagasse fibre, which are biodegradable, have been prepared and characterised by gravimetric analysis for moisture uptake, X-ray powder diffraction for crystallinity, and tensile testing for mechanical properties. Results have shown that the addition of bagasse fibre (5 wt%, 10 wt% or 20 wt%) to either (modified) potato starch (Soluble starch) or hydroxypropylated maize starch reduced moisture uptake by up to 30% at 58% relative humidity (RH). Also, the tensile strength and the Young’s Modulus increased up to 63% and 80% respectively, with the maximum value obtained with 5 wt% fibre at 58% RH. However, the tensile strain of the films significantly decreased by up to 84%. The results have been explained based on the crystallinity of the films and the intrinsic properties of starch and bagasse fibres.

Moisture and tensile strength properties of starch-sugar cane nanofibre films

There is an increasing need for biodegradable, environmentally friendly plastics to replace the petroleum-based non-degradable plastics which litter and pollute the environment. Starch-based plastic film composites are becoming a popular alternative because of their low cost, biodegradability, the abundance of starch, and ease with which starch-based films can be chemically modified. This paper reports on the results of using sugar cane bagasse nanofibres to improve the physicochemical properties of starch-based polymers. The addition of bagasse nanofibre (2.5, 5, 10 or 20 wt%) to (modified) potato starch (‘Soluble starch’) reduced the moisture uptake by up to 17 % at 58 % relative humidity (RH). The film’s tensile strength and Young’s Modulus increased by up to 100 % and 200 % with 10 wt% and 20 wt% nanofibre respectively at 58% RH. The tensile strain reduced by up to 70 % at 20 wt% fibre loading. These results indicate that addition of sugar cane bagasse nanofibres significantly improved the properties of starch-based plastic films

Thermal extrusion of starch film with alcohol

A one-step thermal extrusion process has been investigated for the modification of starch with alcohol in order to improve the film properties. Unmodified starch/glycerol mixtures containing Methanol (MetOH), ethanol (EtOH) and their combinations (5, 10 and 15 wt%) were thermally extruded to produce thermoplastic. The final hot-pressed film showed increased stiffness and crystallinity, while having decreased moisture uptake due to oxidation and alcohol complexing molecular interactions. The Young’s Modulus, tensile strength and elongation at break increased by 60%, 15% and 32% respectively, for 5 wt% MetOH derived film, compared to the control. The film moisture content was reduced by up to 15 wt% for 5 wt% EtOH-derived film. Generally the crystallinity increased in the alcohol-derived films due to an increased complexing of alcohol with starch forming the VH polymorph. Fourier transform infra-red (FTIR) and proton nuclear magnetic resonance (1HNMR) spectroscopic analysis were used to discuss the molecular interactions between the starch and alcohol molecules.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

The influence of mesoporous silica in low T-g cyclic olefin copolymer nanocomposite films: Mechanical and moisture barrier studies

In this study, mesoporous silica-cyclic olefin copolymer nanocomposite films were fabricated by solution casting. With an increase in silica loading, the stiffness of the matrix increased. The nanocomposite film shows increased strain to failure with moisture after aging by matrix plasticization. The storage modulus and loss factor for samples with silica content show better results compared with pristine polymer, as indicated by dynamic mechanical analysis. The interaction between filler-polymer chain exhibit hydrophobicity compared to the neat polymer. Water absorption studies at room temperature and near the T-g of the polymer (similar to 64 degrees C) were carried out. The nanocomposites up to 4 wt% filler reduces the water diffusion by forming hydrogen and chemical bonding. The result by calcium degradation test method for moisture permeability and Schottky structured organic device encapsulation under weathering condition confirms the effective reinforcement effect of silica particles in the matrix. (C) 2014 Elsevier Ltd. All rights reserved.

Effect of silane functionalized alumina on poly(vinyl butyral) nanocomposite films: Thermal, mechanical, and moisture barrier studies

In this work, a hybrid-polymer nanocomposite film, based on polyvinyl butyral/amino-silane functionalized nano alumina, was fabricated by melt processing. The calcium degradation measurements suggest the functionalized nanocomposite films exhibit higher resistance towards moisture penetration as compared to the neat alumina loaded films. Thermal stability, mechanical strength, and contact angle studies of the composites were also conducted to evaluate the performance of the functionalized alumina loaded films. These nanocomposite films were encapsulated over Al/P3HT/ITO Schottky structured device. The changes observed in the current density of the devices to the applied voltage before and after accelerated aging conditions are presented. The nanocomposite with functionalized alumina films exhibits 50% change in current density, which is superior to that attained with neat and non-functionalized films. POLYM. COMPOS., 35:1426-1435, 2014. (c) 2013 Society of Plastics Engineers

Moisture Effects on the Reliability of Anisotropic Conductive Films

Anisotropic conductive film (ACF) which consists of an adhesive epoxy matrix and randomly distributed conductive particles are widely used as the connection material for electronic devices with high I/O counts. However, for the semiconductor industry the reliability of the ACF is still a major concern due to a lack of experimental reliability data. This paper reports an investigation into the moisture effects on the reliability of ACF interconnections in the flip-chip-on-flex (FCOF) applications. A macro-micro 3D finite element modeling technique was used in order to make the multi-length-scale modeling of the ACF flip chip possible. The purposes of this modeling work was to understand the role that moisture plays in the failure of ACF flip chips, and to look into the influence of physical properties and geometric characteristics, such as the coefficient of the moisture expansion (CME), Young's modulus of the adhesive matrix and the bump height on the reliability of the ACF interconnections in a humid environment. Simulation results suggest that moisture-induced swelling of the adhesive matrix is the major cause of the ACF joint opening. Modeling results are consistent with the findings in the experimental work.

Macro-micro modelling of moisture induced stresses in an ACF flip chip assembly

Purpose – This paper discusses the use of modelling techniques to predict the reliability of an anisotropic conductive film (ACF) flip chip in a humid environment. The purpose of this modelling work is to understand the role that moisture plays in the failure of ACF flip chips. Design/methodology/approach – A 3D macro-micro finite element modelling technique was used to determine the moisture diffusion and moisture-induced stresses inside the ACF flip chip. Findings – The results show that the ACF layer in the flip chip can be expected to be fully saturated with moisture after 3?h at 121°C, 100%RH, 2?atm test conditions. The swelling effect of the adhesive due to this moisture absorption causes predominately tensile stress at the interface between the adhesive and the metallization, which could cause a decrease in the contact area, and therefore an increase in the contact resistance. Originality/value – This paper introduces a macro-micro modelling technique which enables more detailed 3D modelling analysis of an ACF flip chip than previously.

Development and Evaluation of a Novel pH Indicator Biodegradable Film Based on Cassava Starch

A pH indicator film based on cassava starch plasticized with sucrose and inverted sugar and incorporated with grape and spinach extracts as pH indicator sources (anthocyanin and chlorophyll) has been developed, and its packaging properties have been assessed. A second-order central composite design (2(2)) with three central points and four star points was used to evaluate the mechanical properties (tensile strength, tensile strength at break, and elongation at break percentage), moisture barrier, and microstructure of the films, and its potential as a pH indicator packaging. The films were prepared by the casting technique and conditioned under controlled conditions (75% relative humidity and 23 degrees C), at least 4 days before the analyses. The materials were exposed to different pH solutions (0, 2, 7, 10, and 14) and their color parameters (L*, a*, b*, and haze) were measured by transmittance. Grape and spinach extracts have affected the material characterization. Film properties (mechanical properties and moisture barrier) were strongly influenced by extract concentration presenting lower results than for the control. Films containing a higher concentration of grape extract presented a greater color change at different pH`s suggesting that anthocyanins are more effective as pH indicators than chlorophyll or the mixture of both extracts. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 1069-1079,2011