A general one-pot strategy for the synthesis of high-performance transparent-conducting-oxide nanocrystal inks for all-solution-processed devices

For all-solution-processed (ASP) devices, transparent conducting oxide (TCO) nanocrystal (NC) inks are anticipated as the next-generation electrodes to replace both those synthesized by sputtering techniques and those consisting of rare metals, but a universal and one-pot method to prepare these inks is still lacking. A universal one-pot strategy is now described; through simply heating a mixture of metal-organic precursors a wide range of TCO NC inks, which can be assembled into high-performance electrodes for use in ASP optoelectronics, were synthesized. This method can be used for various oxide NC inks with yields as high as 10 g. The formed NCs are of high crystallinity, uniform morphology, monodispersity, and high ink stability and feature effective doping. Therefore, the inks can be readily assembled into films with a surface roughness of 1.6 nm. Typically, a sheet resistance of 110 Ω sq-1 can be achieved with a transmittance of 88%, which is the best performance for TCO NC ink-based electrodes described to date. These electrodes can thus drive a polymer light-emitting diode (PLED) with a luminance of 2200 cdm-2 at 100 mA cm-2.

All-fiber noninterferometric narrow-transmission-bandpass filter

In-fiber mode engineering based on the combination of Bragg and long-period gratings (LPGs) permits the implementation of noninterferometric transmission filters with narrow passbands using standard single-mode fiber. The design of the bandpass filter is based on the coupling between propagating and counterpropagating cladding modes in two fiber Bragg gratings. A LPG located between the Bragg gratings transfers power from the input fundamental mode to a specific cladding mode and recouples the filtered signal to the output fundamental mode. The filter produces a series of narrow passbands of about 30 pm linewidth with a maximum transmittance above 60%, 20 dB isolation, and passband separation of about 1 nm, each corresponding to the contribution of a different cladding mode. © 2012 Optical Society of America.

Leaf Optical Properties of Rainforest Sun and Extreme Shade Plants

The opticalp ropertieso f the leaves of twelve tropicals un speciesa nd thirteent ropicale xtreme shade species were examinedw ith an integratings pherea ttachedt o a spectroradiometerM. easurements of diffuse reflectance and transmittance allowed calculations of absorptance, 350- 1,100 nm. Althoughs ome shade species absorbedh igherp ercentageso f quantumf lux densities for photosynthesis (400-700 nm, PPFD) than the mean for the sun species, the sun and shade species as groups were not significantly different from each other: 90.2, S.D. 3.6% for shade species and 88.6, S.D. 2.4% for the sun species. The groups of species did not differ in total absorptance of energy 350-1,100 nm. Furthermore, the sun and shade species were identical in theirs hifto f absorptancea t wavelengthsb etween6 50 and 750 nm. The anthocyanicc oloration of the leaf undersurfaceso f two species polymorphicf or this characteristic( Trionela hirsuta and Ischnosciphonp ruinosus)i s correlatedw ith increaseda bsorptancea t the uppere nd of the action spectrum of photosynthesis. Although sun and shade species have similar optical properties, the energy investment (as documented by dry wt per unit area of leaf surface) is much less for the shade species.

The significance of chloroplast movement in leaves of tropical plants

The purpose of this research project was to contribute to the understanding of chloroplast movement in plants. Chloroplast movement in leaves from twenty tropical plant species ranging from cycads to monocots and varying in shade tolerance was examined by measuring changes in transmittance following 30 min. of exposure to white light at 1000 μmol m−2 s −1 in the wavelength range of 400–700 nm (photosynthetically active radiation, PAR). Leaf anatomical characteristics were also measured. Eighteen species increased significantly in transmittance (Δ T) at this level of illumination. ^ Chloroplast movement was significantly correlated with palisade cell width suggesting that cell dimensions are a significant constraint on chloroplast movement in the species examined. In addition, Δ T values were strongly correlated with values of an index of shade tolerance. ^ To further examine the relationship between palisade width and chloroplast movement, additional studies were conducted with a tropical aroid vine, Scindapsus aureus Schott. Scindapsus plants were grown under three different light treatments: 63% (control), 9.0% and 2.7% of full sunlight. Under these growing conditions plants produced markedly different palisade cell widths. Palisade cell width was again found to be correlated with transmittance changes. In addition, the observed increases in transmittance following exposure to the above illumination condition were correlated with absorbance of PAR. Fluorescence studies demonstrated that chloroplast movement helps protect Scindapsus aureus from the effects of photoinhibition when it is exposed to light at a higher intensity relative to the intensity of its normal environment. Ratios of variable fluorescence (Fv) to maximal fluorescence (Fm ) were higher in plants exposed to high light when chloroplasts moved than in plants where chloroplasts did not. ^ To further explore the role of chloroplast movement, studies were conducted to determine if transmittance changes could be induced in ten xerophytes at (1000 μmol m−2 s−1), as well as two stronger light intensities (1800 μmol m−2 s−1 and 2200 μmol m−2 s −1). Transmittance changes in the ten xerophytes were dependent upon the illumination intensity; nine out of the ten xerophytes changed in transmittance at 1800 μmol m−2 s−1. For the other two intensity levels, only three out of the ten xerophytes tested exhibited transmittance changes, and for two species, a negative Δ T value was obtained at 1000 μmol m−2 s−1 . No relationship was found between cell dimensions and chloroplast movement, although all species had large enough chlorenchyma cells to allow such movements. ^ The results of the study clearly show that in non-xerophytes, palisade cell anatomy is a strong constraint on chloroplast movement. This relationship may be the basis for the relationship between chloroplast movement and shade tolerance. Although absorbance changes are relatively small, chloroplast movement was clearly shown to reduce photoinhibition. ^

The successional dynamics of lightning-initiated canopy gaps in the mangrove forests of Shark River, Everglades National Park, USA

Gap succession is a significant determinant of structure and development in most forest communities. Lightning strikes are an important source of canopy gaps in the mangrove forest of Everglades National Park. I investigated the successional dynamics of lightning-initiated canopy gaps to determine their influence on forest stand structure of the mixed mangrove forests ( Rhizophora mangle, Laguncularia racemosa, and Avicennia germinans ) of the Shark River. I measured gap size, gap shape, light environment, soil characteristics, woody debris, and fiddler crab abundance. I additionally measured the vegetative composition in a chronosequences of gap successional stages (new, recruiting, and growing gaps). I recorded survivorship, recruitment, growth and soil elevation dynamics within a subset of new and growing gaps. I determined the relationship between intact forest soil elevation and site hydrology in order to interpret the effects of lightning disturbance on soil elevation dynamics. ^ Gap size averaged 289 ± 20 m2 (± 1SE) and light transmittance decreased exponentially as gaps filled with saplings. Fine woody debris was highest in recruiting gaps. Soil strength was lower in the gaps than in the forest. The abundance of large and medium fiddler crab burrows increased linearly with total seedling abundance. Soil surface elevation declined in newly formed lightning gaps; this loss was due to a combination of superficial erosion (8.5 mm) and subsidence (60.9 mm). A distinct two-cohort recruitment pattern was evident in the seedling/sapling surveys, suggesting a partitioning of the succession between individuals present before and after lightning strike. In new gaps, the seedling recruitment rate was twice as high as in forest and the sapling population increased. At the growing gap stage, R. mangle seedling mortality was 10 times greater and sapling mortality was 13 times greater than recruitment. Growing gaps had reduced seedling stem elongation, sapling growth and adult growth. However, a few individuals (R. mangle saplings) were able to recruit into the adult life stage. In conclusion, the high density of R. mangle seedlings and saplings imply that lightning strike disturbances in these mangrove forests favor their recruitment over that of A. germinans and L. racemosa. ^

Enhanced zinc oxide and graphene nanostructures for electronics and sensing applications

Zinc oxide and graphene nanostructures are important technological materials because of their unique properties and potential applications in future generation of electronic and sensing devices. This dissertation investigates a brief account of the strategies to grow zinc oxide nanostructures (thin film and nanowire) and graphene, and their applications as enhanced field effect transistors, chemical sensors and transparent flexible electrodes. Nanostructured zinc oxide (ZnO) and low-gallium doped zinc oxide (GZO) thin films were synthesized by a magnetron sputtering process. Zinc oxide nanowires (ZNWs) were grown by a chemical vapor deposition method. Field effect transistors (FETs) of ZnO and GZO thin films and ZNWs were fabricated by standard photo and electron beam lithography processes. Electrical characteristics of these devices were investigated by nondestructive surface cleaning, ultraviolet irradiation treatment at high temperature and under vacuum. GZO thin film transistors showed a mobility of ∼5.7 cm2/V·s at low operation voltage of <5 V and a low turn-on voltage of ∼0.5 V with a sub threshold swing of ∼85 mV/decade. Bottom gated FET fabricated from ZNWs exhibit a very high on-to-off ratio (∼106) and mobility (∼28 cm2/V·s). A bottom gated FET showed large hysteresis of ∼5.0 to 8.0 V which was significantly reduced to ∼1.0 V by the surface treatment process. The results demonstrate charge transport in ZnO nanostructures strongly depends on its surface environmental conditions and can be explained by formation of depletion layer at the surface by various surface states. A nitric oxide (NO) gas sensor using single ZNW, functionalized with Cr nanoparticles was developed. The sensor exhibited average sensitivity of ∼46% and a minimum detection limit of ∼1.5 ppm for NO gas. The sensor also is selective towards NO gas as demonstrated by a cross sensitivity test with N2, CO and CO2 gases. Graphene film on copper foil was synthesized by chemical vapor deposition method. A hot press lamination process was developed for transferring graphene film to flexible polymer substrate. The graphene/polymer film exhibited a high quality, flexible transparent conductive structure with unique electrical-mechanical properties; ∼88.80% light transmittance and ∼1.1742Ω/sq k sheet resistance. The application of a graphene/polymer film as a flexible and transparent electrode for field emission displays was demonstrated.

Effects of shading on calcareous benthic periphyton in a short-hydroperiod oligotrophic wetland (Everglades, FL, USA)

The effects of shade on benthic calcareous periphyton were tested in a short-hydroperiod oligotrophic subtropical wetland (freshwater Everglades). The experiment was a split-plot design set in three sites with similar environmental characteristics. At each site, eight randomly selected 1-m2 areas were isolated individually in a shade house, which did not spectrally change the incident irradiance but reduced it quantitatively by 0, 30, 50, 60, 70, 80, 90 and 98%. Periphyton mat was sampled monthly under each shade house for a 5 month period while the wetland was flooded. Periphyton was analyzed for thickness, DW, AFDW, chlorophyll a (chl a) and incubated in light and dark BOD bottles at five different irradiances to assess its photosynthesis–irradiance (PI) curve and respiration. The PI curves parameters P max, I k and eventually the photoinhibition slope (β) were determined following non-linear regression analyses. Taxonomic composition and total algal biovolume were determined at the end of the experiment. The periphyton composition did not change with shade but the PI curves were significantly affected by it. I k increased linearly with increasing percent irradiance transmittance (%IT = 1−%shade). P max could be fitted with a PI curve equation as it increased with %IT and leveled off after 10%IT. For each shade level, the PI curve was used to integrate daily photosynthesis for a day of average irradiance. The daily photosynthesis followed a PI curve equation with the same characteristics as P max vs. %IT. Thus, periphyton exhibited a high irradiance plasticity under 0–80% shade but could not keep up the same photosynthetic level at higher shade, causing a decrease in daily GPP at 98% shade levels. The plasticity was linked to an increase in the chl a content per cell in the 60–80% shade, while this increase was not observed at lower shade likely because it was too demanding energetically. Thus, chl a is not a good metric for periphyton biomass assessment across variously shaded habitats. It is also hypothesized that irradiance plasticity is linked to photosynthetic coupling between differently comprised algal layers arranged vertically within periphyton mats that have different PI curves.

Acoustic Manipulation and Alignment of Particles for Applications in Separation, Micro-Templating, and Device Fabrication

This dissertation studies the manipulation of particles using acoustic stimulation for applications in microfluidics and templating of devices. The term particle is used here to denote any solid, liquid or gaseous material that has properties, which are distinct from the fluid in which it is suspended. Manipulation means to take over the movements of the particles and to position them in specified locations. Using devices, microfabricated out of silicon, the behavior of particles under the acoustic stimulation was studied with the main purpose of aligning the particles at either low-pressure zones, known as the nodes or high-pressure zones, known as anti-nodes. By aligning particles at the nodes in a flow system, these particles can be focused at the center or walls of a microchannel in order to ultimately separate them. These separations are of high scientific importance, especially in the biomedical domain, since acoustopheresis provides a unique approach to separate based on density and compressibility, unparalleled by other techniques. The study of controlling and aligning the particles in various geometries and configurations was successfully achieved by controlling the acoustic waves. Apart from their use in flow systems, a stationary suspended-particle device was developed to provide controllable light transmittance based on acoustic stimuli. Using a glass compartment and a carbon-particle suspension in an organic solvent, the device responded to acoustic stimulation by aligning the particles. The alignment of light-absorbing carbon particles afforded an increase in visible light transmittance as high as 84.5%, and it was controlled by adjusting the frequency and amplitude of the acoustic wave. The device also demonstrated alignment memory rendering it energy-efficient. A similar device for suspended-particles in a monomer enabled the development of electrically conductive films. These films were based on networks of conductive particles. Elastomers doped with conductive metal particles were rendered surface conductive at particle loadings as low as 1% by weight using acoustic focusing. The resulting films were flexible and had transparencies exceeding 80% in the visible spectrum (400-800 nm) These films had electrical bulk conductivities exceeding 50 S/cm.

Radiation fluxes, soil heat flux, air temperature, soil temperature, soil moisture and vegetation at dwarf shrubs and wet sedges in Kytalyk, NE Siberia

Vegetation changes, such as shrub encroachment and wetland expansion, have been observed in many Arctic tundra regions. These changes feed back to permafrost and climate. Permafrost can be protected by soil shading through vegetation as it reduces the amount of solar energy available for thawing. Regional climate can be affected by a reduction in surface albedo as more energy is available for atmospheric and soil heating. Here, we compared the shortwave radiation budget of two common Arctic tundra vegetation types dominated by dwarf shrubs (Betula nana) and wet sedges (Eriophorum angustifolium) in North-East Siberia. We measured time series of the shortwave and longwave radiation budget above the canopy and transmitted radiation below the canopy. Additionally, we quantified soil temperature and heat flux as well as active layer thickness. The mean growing season albedo of dwarf shrubs was 0.15 ± 0.01, for sedges it was higher (0.17 ± 0.02). Dwarf shrub transmittance was 0.36 ± 0.07 on average, and sedge transmittance was 0.28 ± 0.08. The standing dead leaves contributed strongly to the soil shading of wet sedges. Despite a lower albedo and less soil shading, the soil below dwarf shrubs conducted less heat resulting in a 17 cm shallower active layer as compared to sedges. This result was supported by additional, spatially distributed measurements of both vegetation types. Clouds were a major influencing factor for albedo and transmittance, particularly in sedge vegetation. Cloud cover reduced the albedo by 0.01 in dwarf shrubs and by 0.03 in sedges, while transmittance was increased by 0.08 and 0.10 in dwarf shrubs and sedges, respectively. Our results suggest that the observed deeper active layer below wet sedges is not primarily a result of the summer canopy radiation budget. Soil properties, such as soil albedo, moisture, and thermal conductivity, may be more influential, at least in our comparison between dwarf shrub vegetation on relatively dry patches and sedge vegetation with higher soil moisture.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Design of Transparent Conducting Electrodes and Surface Relief Gratings for Plasmonic Polymer Solar Cells

As the concept of renewable energy becomes increasingly important in the modern society, a considerable amount of research has been conducted in the field of organic photovoltaics in recent years. Although organic solar cells generally have had lower efficiencies compared to silicon solar cells, they have the potential to be mass produced via solution processing. A common polymer solar cell architecture relies on the usage of P3HT (electron donor) and PCBM (electron acceptor) bulk heterojunction. One of the main issues with this configuration is that in order to compensate for the high exciton recombination rate, the photoactive layer is often made very thin (on the order of 100 $%). This results in low solar cell photocurrents due to low absorption. This thesis investigates a novel method of light trapping by coupling surface plasmons at the electrode interface via surface relief gratings, leading to EM field enhancements and increased photo absorption. Experimental work was first conducted on developing and optimizing a transparent electrode of the form &'()/+,/&'() to replace the traditional ITO electrode since the azopolymer gratings cannot withstand the high temperature processing of ITO films. It was determined that given the right thickness profiles and deposition conditions, the MAM stack can achieve transmittance and conductivity similar to ITO films. Experimental work was also conducted on the fabrication and characterization of surface relief gratings, as well as verification of the surface plasmon generation. Surface relief gratings were fabricated easily and accurately via laser interference lithography on photosensitive azopolymer films. Laser diffraction studies confirmed the grating pitch, which is dependent on the incident angle and wavelength of the writing beam. AFM experiments were conducted to determine the surface morphology of the gratings, before and after metallic film deposition. It was concluded that metallic film deposition does not significantly alter the grating morphologies.

Design of Transparent Conducting Electrodes and Surface Relief Gratings for Plasmonic Polymer Solar Cells

As the concept of renewable energy becomes increasingly important in the modern society, a considerable amount of research has been conducted in the field of organic photovoltaics in recent years. Although organic solar cells generally have had lower efficiencies compared to silicon solar cells, they have the potential to be mass produced via solution processing. A common polymer solar cell architecture relies on the usage of P3HT (electron donor) and PCBM (electron acceptor) bulk heterojunction. One of the main issues with this configuration is that in order to compensate for the high exciton recombination rate, the photoactive layer is often made very thin (on the order of 100 $%). This results in low solar cell photocurrents due to low absorption. This thesis investigates a novel method of light trapping by coupling surface plasmons at the electrode interface via surface relief gratings, leading to EM field enhancements and increased photo absorption. Experimental work was first conducted on developing and optimizing a transparent electrode of the form &'()/+,/&'() to replace the traditional ITO electrode since the azopolymer gratings cannot withstand the high temperature processing of ITO films. It was determined that given the right thickness profiles and deposition conditions, the MAM stack can achieve transmittance and conductivity similar to ITO films. Experimental work was also conducted on the fabrication and characterization of surface relief gratings, as well as verification of the surface plasmon generation. Surface relief gratings were fabricated easily and accurately via laser interference lithography on photosensitive azopolymer films. Laser diffraction studies confirmed the grating pitch, which is dependent on the incident angle and wavelength of the writing beam. AFM experiments were conducted to determine the surface morphology of the gratings, before and after metallic film deposition. It was concluded that metallic film deposition does not significantly alter the grating morphologies.

Synthesis and characterization of Tellurium oxide glasses for photonic applications

Tellurite glasses are photonic materials of special interest to the branch of optoelectronic and communication, due to its important optical properties such as high refractive index, broad IR transmittance, low phonon energy etc. Tellurite glasses are solutions to the search of potential candidates for nonlinear optical devices. Low phonon energy makes it an efficient host for dopant ions like rare earths, allowing a better environment for radiative transitions. The dopant ions maintain majority of their individual properties in the glass matrix. Tellurites are less toxic than chalcogenides, more chemically and thermally stable which makes them a highly suitable fiber material for nonlinear applications in the midinfrared and they are of increased research interest in applications like laser, amplifier, sensor etc. Low melting point and glass transition temperature helps tellurite glass preparation easier than other glass families.In order to probe into the versatility of tellurite glasses in optoelectronic industry; we have synthesized and undertaken various optical studies on tellurite glasses. We have proved that the highly nonlinear tellurite glasses are suitable candidates in optical limiting, with comparatively lower optical limiting threshold. Tuning the optical properties of glasses is an important factor in the optoelectronic research. We have found that thermal poling is an efficient mechanism in tuning the optical properties of these materials. Another important nonlinear phenomenon found in zinc tellurite glasses is their ability to switch from reverse saturable absorption to saturable absorption in the presence of lanthanide ions. The proposed thesis to be submitted will have seven chapters.

Análise do custo-benefício de sistemas de cobertas em edificações comerciais para o clima de Natal/RN visando eficiência energética

This research consists in studying the influence of the various type of construction systems of roofs with their energy efficiency as well as on the cost benefit for the commercial buildings on the temperatures condition of the city of Natal/RN. The main goal of this research is to analyze the cost benefit of the construction systems of roofs available on the market, taking into consideration the energy efficiency of the commercial buildings artificially air conditioned in order to be used by the projectors and to be adequated to the temperatures condition of the city of Natal/RN. The method of valuation of the cost benefit of roof systems consists in six steps: Features and simulation of the reference building; Analyze of sensitivity; Analyzes, features and simulation of alternatives of roof construction systems; Analyze of the cost of implementation; Analyze of the benefits of the alternatives comparing to the base case; And finally the analyze of the cost benefit. The model type chosen as reference was stores with pre molded buildings and system of roof with fiber ciment and ceiling . The thermal results showed the influence of the roof system on the energy efficiency of the building. The Final results of the simulations of the alternatives comes to a conclusion that the absortance is the variable that presents the best cost benefit relation and the reduction on the thermal transmittance still has limitations because of the high cost

Análise de métodos de predição de conforto térmico de habitação em clima quente-úmido com condicionamento passivo

The assessment of building thermal performance is often carried out using HVAC energy consumption data, when available, or thermal comfort variables measurements, for free-running buildings. Both types of data can be determined by monitoring or computer simulation. The assessment based on thermal comfort variables is the most complex because it depends on the determination of the thermal comfort zone. For these reasons, this master thesis explores methods of building thermal performance assessment using variables of thermal comfort simulated by DesignBuilder software. The main objective is to contribute to the development of methods to support architectural decisions during the design process, and energy and sustainable rating systems. The research method consists on selecting thermal comfort methods, modeling them in electronic sheets with output charts developed to optimize the analyses, which are used to assess the simulation results of low cost house configurations. The house models consist in a base case, which are already built, and changes in thermal transmittance, absorptance, and shading. The simulation results are assessed using each thermal comfort method, to identify the sensitivity of them. The final results show the limitations of the methods, the importance of a method that considers thermal radiance and wind speed, and the contribution of the chart proposed