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1.
J Chem Phys ; 158(3): 034702, 2023 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-36681626

RESUMO

Silica-based aerogels are a promising low-cost solution for improving the insulation efficiency of single-pane windows and reducing the energy consumption required for space heating and cooling. Two key material properties required are high porosity and small pore sizes, which lead to low thermal conductivity and high optical transparency, respectively. However, porosity and pore size are generally directly linked, where high porosity materials also have large pore sizes. This is unfavorable as large pores scatter light, resulting in reduced transmittance in the visible regime. In this work, we utilized preformed silica colloids to explore methods for reducing pore size while maintaining high porosity. The use of preformed colloids allows us to isolate the effect of solution conditions on porous gel network formation by eliminating simultaneous nanoparticle growth and aggregation found when using typical sol-gel molecular-based silica precursors. Specifically, we used in situ synchrotron-based small-angle x-ray scattering during gel formation to better understand how pH, concentration, and colloid size affect particle aggregation and pore structure. Ex situ characterization of dried gels demonstrates that peak pore widths can be reduced from 15 to 13 nm, accompanied by a narrowing of the overall pore size distribution, while maintaining porosities of 70%-80%. Optical transparency is found to increase with decreasing pore sizes while low thermal conductivities ranging from 95 +/- 13 mW/m K are maintained. Mechanical performance was found to depend primarily on effective density and did not show a significant dependence on solution conditions. Overall, our results provide insights into methods to preserve high porosity in nanoparticle-based aerogels while improving optical transparency.


Assuntos
Nanopartículas , Dióxido de Silício , Dióxido de Silício/química , Raios X , Géis/química , Coloides , Porosidade
2.
J Am Chem Soc ; 144(13): 5841-5854, 2022 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-35333056

RESUMO

Electrode materials for Li+-ion batteries require optimization along several disparate axes related to cost, performance, and sustainability. One of the important performance axes is the ability to retain structural integrity though cycles of charge/discharge. Metal-metal bonding is a distinct feature of some refractory metal oxides that has been largely underutilized in electrochemical energy storage, but that could potentially impact structural integrity. Here LiScMo3O8, a compound containing triangular clusters of metal-metal bonded Mo atoms, is studied as a potential anode material in Li+-ion batteries. Electrons inserted though lithiation are localized across rigid Mo3 triangles (rather than on individual metal ions), resulting in minimal structural change as suggested by operando diffraction. The unusual chemical bonding allows this compound to be cycled with Mo atoms below a formally +4 valence state, resulting in an acceptable voltage regime that is appropriate for an anode material. Several characterization methods including potentiometric entropy measurements indicate two-phase regions, which are attributed through extensive first-principles modeling to Li+ ordering. This study of LiScMo3O8 provides valuable insights for design principles for structural motifs that stably and reversibly permit Li+ (de)insertion.

3.
Langmuir ; 33(37): 9407-9415, 2017 09 19.
Artigo em Inglês | MEDLINE | ID: mdl-28545299

RESUMO

Composite structures for electrochemical energy storage are prepared on the basis of using the high-rate lithium ion insertion properties of Nb2O5. The Nb2O5 is anchored on reduced graphene oxide (rGO) by hydrothermal synthesis to improve the charge-transfer properties, and by controlling the surface charge, the resulting Nb2O5-rGO particles are attached to a high-surface-area carbide-derived carbon scaffold without blocking its exfoliated layers. The electrochemical results are analyzed using a recently published multiscale physics model that provides significant insights regarding charge storage kinetics. In particular, the composite electrode exhibits surface-confined charge storage at potentials of <1.7 V (vs Li/Li+), where faradaic processes dominate, and electrical double layer charge storage at potentials of >2.2 V. A hybrid device composed of the composite electrode with activated carbon as the positive electrode demonstrates increased energy density at power densities comparable to an activated carbon device, provided the hybrid device operates in the faradaic potential range.

4.
J Opt Soc Am A Opt Image Sci Vis ; 33(8): 1495-503, 2016 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-27505647

RESUMO

This study aims to answer the question of whether spherical unicellular photoautotrophic eukaryotic microalgae cells, consisting of various intracellular compartments with their respective optical properties, can be modeled as homogeneous spheres with some effective complex index of refraction. The spectral radiation characteristics in the photosynthetically active region of a spherical heterogeneous microalgae cell, representative of Chlamydomonas reinhardtii and consisting of spherical compartments corresponding to the cell wall, cytoplasm, chloroplast, nucleus, and mitochondria, were estimated using the superposition T-matrix method. The effects of the presence of intracellular lipids and/or starch accumulation caused by stresses, such as nitrogen limitation, were explored. Predictions by the T-matrix method were qualitatively and quantitatively consistent with experimental measurements for various microalgae species. The volume-equivalent homogeneous sphere approximation with volume-averaged effective complex index of refraction gave accurate estimates of the spectral (i) absorption and (ii) scattering cross sections of the heterogeneous cells under both nitrogen-replete and nitrogen-limited conditions. In addition, the effect of a strongly refracting cell wall, representative of Chlorella vulgaris, was investigated. In this case, for the purpose of predicting their integral radiation characteristics, the microalgae should be represented as a coated sphere with a coating corresponding to the cell wall and a homogeneous core with volume-averaged complex index of refraction for the rest of the cell. However, both homogeneous sphere and coated sphere approximations predicted strong resonances in the scattering phase function and spectral backscattering cross section that were not observed in that of the heterogeneous cells.


Assuntos
Chlamydomonas reinhardtii/citologia , Chlorella vulgaris/citologia , Microalgas/citologia , Fenômenos Ópticos , Proliferação de Células , Parede Celular/metabolismo
5.
J Opt Soc Am A Opt Image Sci Vis ; 32(1): 46-60, 2015 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-26366489

RESUMO

This study demonstrates that the absorption and scattering cross sections and asymmetry factor of randomly oriented and optically soft bispheres, quadspheres, and circular rings of spheres, with either monodisperse or polydisperse monomers, can be approximated by an equivalent coated sphere with identical volume and average projected area. This approximation could also apply to the angle-dependent scattering matrix elements for monomer size parameter less than 0.1. However, it quickly deteriorated with increasing monomer number and/or size parameter. It was shown to be superior to previously proposed approximations considering a volume equivalent homogeneous sphere and a coated sphere with identical volume and surface area. These results provide a rapid and accurate way of predicting the radiation characteristics of bispheres, quadspheres, and rings of spheres representative of various unicellular and multicellular cyanobacteria considered for producing food supplements, biofuels, and fertilizers. They could also be used in inverse methods for retrieving the monomers' optical properties, morphology, and/or concentration.


Assuntos
Absorção de Radiação , Cianobactérias/efeitos da radiação , Espalhamento de Radiação , Fotobiorreatores/microbiologia
6.
Appl Opt ; 54(19): 6116-7, 2015 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-26193161

RESUMO

A previous paper [Appl. Opt.48, 6670 (2009)] presented analytical expressions for the diffuse reflectance of semi-infinite homogeneous and two-layer refracting, absorbing, and anisotropically scattering media exposed to normal and collimated light. It also reported various regression coefficients associated with the analytical expressions obtained by fitting the diffuse reflectance predicted from Monte Carlo (MC) simulations. Although the formulation and the MC simulation results were correct, the values of some regression coefficients were erroneously reported. This erratum points out the error in the original paper and reports the correct values. It also presents alternative expressions for when the medium has an index of refraction of 1.44, corresponding to the human skin in the visible portion of the spectrum.

7.
J Opt Soc Am A Opt Image Sci Vis ; 31(4): 836-45, 2014 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-24695147

RESUMO

This study presents experimental measurements of the absorption and scattering cross sections and the spectral complex index of refraction of filamentous cyanobacteria. Filamentous heterocystous cyanobacterium Anabaena cylindrica was chosen as a model organism. Its filaments consisted of long chains of polydisperse cells. Their average mass scattering and absorption cross sections were measured from 400 to 750 nm at four different times during their batch growth in medium BG-11(-N) under 3000 lux of white fluorescent light. The effective real (or refraction index) and imaginary (or absorption index) parts of the complex index of refraction were retrieved using an inverse method based on a genetic algorithm. The microorganisms were modeled as infinitely long and randomly oriented volume-equivalent cylinders. The absorption index featured peaks corresponding to chlorophyll a (Chl a) at 436 and 676 nm and phycocyanin (PCCN) at 630 nm and a shoulder around 480 nm, corresponding to photoprotective carotenoids. The absorption peaks of Chl a and PCCN concentrations increased and the shoulder due to carotenoids decreased in response to photolimitation caused by biomass growth. Subsequent nitrogen limitation caused the PCCN absorption peak to decrease significantly due to degradation of PCCN as an endogenous source of nitrogen for nitrogenase maintenance and synthesis, as confirmed by increasing heterocyst differentiation. The results can be used for predicting and optimizing light transfer in photobioreactors for wastewater treatment and ammonia or biofuel production.


Assuntos
Anabaena cylindrica/metabolismo , Luz , Fenômenos Ópticos , Absorção , Fotossíntese , Espalhamento de Radiação
8.
J Phys Chem C Nanomater Interfaces ; 128(15): 6419-6430, 2024 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-38655060

RESUMO

Concentrated and thick oil-in-water nanoemulsions have been observed to become more transparent with increasing oil volume fraction. This study demonstrates rigorously experimentally and numerically that such unusual behavior is due to dependent scattering including not only far-field but also near-field effects. Indeed, when the droplet concentration is sufficiently large, their interparticle distance becomes small compared to the wavelength of light and scattering by a given droplet may be affected by the proximity of others. This situation is referred to as dependent scattering. Light transfer through nanoemulsions and other colloids has previously been modeled by solving the radiative transfer equation accounting for dependent scattering using the static structure factor based on far-field approximations. Here, oil-in-water nanoemulsions were prepared with oil volume fraction ranging between 1 and 20% and a peak droplet radius of 16 nm. The spectral normal-hemispherical transmittance of the different nanoemulsions in 10 mm thick cuvettes was measured experimentally between 400 and 900 nm. Numerical predictions for nonoverlapping randomly distributed nanoscale oil droplets in water and accounting for dependent scattering including near-field effects-using the recently developed radiative transfer with reciprocal transactions (R2T2) method-were in excellent agreement with experimental measurements. Simulations revealed that assuming independent scattering underestimated the normal-hemispherical transmittance even for a relatively small oil volume fraction. Additionally, simulations using the dense medium radiative transfer (DMRT) and static structure factor predicted that dependent scattering prevailed for oil volume fractions slightly greater than those predicted by the R2T2 method. Interestingly, the DMRT method predicted large increases in transmittance when the oil droplet size and volume fraction were larger than 10 nm and 10%, respectively. Finally, simulations also revealed that dependent scattering enables the design of oil-in-water nanoemulsions to backscatter or absorb light by tuning the oil droplet size and volume fraction. The results validate that the R2T2 method could be used to characterize nanoemulsions or to investigate their formation, composition, and stability for drug delivery, food, and cosmetics applications. Future studies could extend the use of the R2T2 method to colloidal suspensions with particles of arbitrary shapes and to radiation transfer of polarized light in turbid media.

9.
ACS Polym Au ; 4(1): 86-97, 2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38371729

RESUMO

We demonstrate facile fabrication of highly filled, lightweight organic-inorganic composites comprising polyurethanes covalently linked with naturally occurring clinoptilolite microparticles. These polyurethane/clinoptilolite (PUC) composites are shown to mitigate particle aggregation usually observed in composites with high particle loadings and possess enhanced thermal insulation and acoustic attenuation compared with conventionally employed materials (e.g., drywall and gypsum). In addition to these functional properties, the PUC composites also possess flexural strengths and strain capacities comparable to and higher than ordinary Portland cement (OPC), respectively, while being ∼1.5× lighter than OPC. The porosity, density, and mechanical and functional properties of these composites are tuned by systematically varying their composition (diisocyanate, polyurethane, and inorganic contents) and the nature of the organic (reactivity and source of polyol) components. The fabrication process involves mild curing conditions and uses commonly available reagents (naturally occurring aluminosilicate particles, polyols, and diisocyanate), thereby making the process scalable. Finally, the composite properties are shown to be independent of the polyol source (virgin or recycled), underlining the generality of this approach for the scalable utilization of recycled polyols.

10.
ACS Appl Polym Mater ; 6(9): 4954-4963, 2024 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-38752015

RESUMO

This study explores the influence of electronic and ionic conductivities on the behavior of conjugated polymer binders through the measurement of entropic potential and heat generation in an operating lithium-ion battery. Specifically, the traditional poly(vinylidene fluoride) (PVDF) binder in LiNi0.8Co0.15Al0.05O2 (NCA) cathode electrodes was replaced with semiconducting polymer binders based on poly(3,4-propylenedioxythiophene). Two conjugated polymers were explored: one is a homopolymer with all aliphatic side chains, and the other is a copolymer with both aliphatic and ethylene oxide side chains. We have shown previously that both polymers have high electronic conductivity in the potential range of NCA redox, but the copolymer has a higher ionic conductivity and a slightly lower electronic conductivity. Entropic potential measurements during battery cycling revealed consistent trends during delithiation for all of the binders, indicating that the binders did not modify the expected NCA solid solution deintercalation process. The entropic signature of polymer doping to form the conductive state could be clearly observed at potentials below NCA oxidation, however. Operando isothermal calorimetric measurements showed that the conductive binders resulted in less Joule heating compared to PVDF and that the net electrical energy was entirely dissipated as heat. In a comparison of the two conjugated polymer binders, the heat dissipation was lower for the homopolymer binder at lower C-rates, suggesting that electronic conductivity rather than ionic conductivity was the most important for reducing Joule heating at lower rates, but that ionic conductivity became more important at higher rates.

11.
J Opt Soc Am A Opt Image Sci Vis ; 30(9): 1892-900, 2013 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-24323271

RESUMO

This paper demonstrates that the scattering cross section per unit length of randomly oriented linear chains of optically soft spheres asymptotically converges toward those of randomly oriented and infinitely long cylinders with volume-equivalent diameter as the number of spheres increases. The critical number of spheres necessary to approximate the linear chains of spheres as infinitely long cylinders decreased rapidly as the size parameter of an individual sphere increased from 0.01 to 10. On the other hand, their absorption cross section per unit length was identical to that of an infinitely long volume-equivalent cylinder for any number of spheres. However, this approximation does not apply to the angle-dependent normalized Stokes scattering matrix element ratios.


Assuntos
Cianobactérias/fisiologia , Absorção , Biofísica/métodos , Reatores Biológicos , Modelos Biológicos , Óptica e Fotônica , Refratometria , Espalhamento de Radiação
12.
J Colloid Interface Sci ; 648: 418-426, 2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37302225

RESUMO

By virtue of their low density and thermal conductivity, aerogels constitute attractive thermal insulators. Of those, aerogel films are best suited for thermal insulation in microsystems. Processes for the synthesis of aerogel films with thicknesses smaller than 2 µm or thicker than 1 mm are well established. However, for microsystems films in the range of a few microns and up to several hundred microns would be beneficial. To circumvent the present limitations, we describe a liquid mold made of two immiscible liquids, used here to produce aerogel films thicker than 2 µm in a single molding step. Following gelation and aging, the gels were removed from the liquids and dried using supercritical carbon dioxide. In contrast to spin/dip coating, liquid molding avoids solvent evaporation from the gel's outer surface during gelation and aging, films are free-standing and have smooth surfaces. The choice of liquids determines the aerogel film thickness. As a proof of concept, 130 µm thick homogeneous and high porosity (>90%) silica aerogel films were synthesized in a liquid mold with fluorine oil and octanol. The resemblance of the liquid mold approach to the float glass technique offers the prospect of mass production of large sheets of aerogel films.

13.
Int J Heat Mass Transf ; 55(25-26): 7823-7831, 2012 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-25552745

RESUMO

The present study reports experimental data and scaling analysis for forced convection of foams and microfoams in laminar flow in circular and rectangular tubes as well as in tube bundles. Foams and microfoams are pseudoplastic (shear thinning) two-phase fluids consisting of tightly packed bubbles with diameters ranging from tens of microns to a few millimeters. They have found applications in separation processes, soil remediation, oil recovery, water treatment, food processes, as well as in fire fighting and in heat exchangers. First, aqueous solutions of surfactant Tween 20 with different concentrations were used to generate microfoams with various porosity, bubble size distribution, and rheological behavior. These different microfoams were flowed in uniformly heated circular tubes of different diameter instrumented with thermocouples. A wide range of heat fluxes and flow rates were explored. Experimental data were compared with analytical and semi-empirical expressions derived and validated for single-phase power-law fluids. These correlations were extended to two-phase foams by defining the Reynolds number based on the effective viscosity and density of microfoams. However, the local Nusselt and Prandtl numbers were defined based on the specific heat and thermal conductivity of water. Indeed, the heated wall was continuously in contact with a film of water controlling convective heat transfer to the microfoams. Overall, good agreement between experimental results and model predictions was obtained for all experimental conditions considered. Finally, the same approach was shown to be also valid for experimental data reported in the literature for laminar forced convection of microfoams in rectangular minichannels and of macrofoams across aligned and staggered tube bundles with constant wall heat flux.

14.
J Colloid Interface Sci ; 606(Pt 1): 884-897, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34454313

RESUMO

This paper presents a novel sol-gel method to synthesize large and thick silica aerogel monoliths at near ambient conditions using a commercial aqueous solution of colloidal silica nanoparticles as building blocks. To achieve slabs with high visible transmittance and low thermal conductivity, the method combines the strategies of (i) synthesizing gels on an omniphobic perfluorocarbon liquid substrate, (ii) aging at temperatures above room temperature, and (iii) performing solvent exchange with a low-surface-tension organic solvent prior to ambient drying. The omniphobic liquid substrates were used to prevent cracking and ensure an optically-smooth surface, while nanoparticle building blocks were small (<10 nm) to limit volumetric light scattering. Gels were aged at temperatures between 25 and 80 °C for up to 21 days to make them stronger and stiffer and to reduce shrinkage and cracking during ambient drying. Ambient drying was achieved by first exchanging water in the gel pores for octane, followed by drying in an octane-rich atmosphere to decrease capillary forces. The synthesized nanoparticle-based silica aerogel monoliths had thicknesses up to 5 mm, diameters up to 10 cm, porosities exceeding 80%, and thermal conductivities as low as 0.08 W m-1 K-1. Notably, the slabs featured visible transmittance exceeding 75% even for slabs as thick as 5 mm. The as-synthesized aerogel monoliths were exposed to TMCS vapor to induce hydrophobic properties resulting in a water contact angle of 140° that prevented water infiltration into the pores and protected the aerogels from water damage. This simple synthesis route conducted at near ambient conditions produces hydrophobic aerogel monoliths with promising optically transparent and thermally insulating properties that can be adhered to glass panes for window insulation and solar-thermal energy conversion applications.


Assuntos
Nanopartículas , Dióxido de Silício , Géis , Suspensões , Condutividade Térmica
15.
RSC Adv ; 11(3): 1762-1772, 2021 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-35424115

RESUMO

Calcium hydroxide (Ca(OH)2), a commodity chemical, finds use in diverse industries ranging from food, to environmental remediation and construction. However, the current thermal process of Ca(OH)2 production via limestone calcination is energy- and CO2-intensive. Herein, we demonstrate a novel aqueous-phase calcination-free process to precipitate Ca(OH)2 from saturated solutions at sub-boiling temperatures in three steps. First, calcium was extracted from an archetypal alkaline industrial waste, a steel slag, to produce an alkaline leachate. Second, the leachate was concentrated using reverse osmosis (RO) processing. This elevated the Ca-abundance in the leachate to a level approaching Ca(OH)2 saturation at ambient temperature. Thereafter, Ca(OH)2 was precipitated from the concentrated leachate by forcing a temperature excursion in excess of 65 °C while exploiting the retrograde solubility of Ca(OH)2. This nature of temperature swing can be forced using low-grade waste heat (≤100 °C) as is often available at power generation, and industrial facilities, or using solar thermal heat. Based on a detailed accounting of the mass and energy balances, this new process offers at least ≈65% lower CO2 emissions than incumbent methods of Ca(OH)2, and potentially, cement production.

16.
Appl Opt ; 49(10): 1707-19, 2010 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-20357850

RESUMO

We present a method to determine chromophore concentrations, blood saturation, and epidermal thickness of human skin from diffuse reflectance spectra. Human skin was approximated as a plane-parallel slab of variable thickness supported by a semi-infinite layer corresponding to the epidermis and dermis, respectively. The absorption coefficient was modeled as a function of melanin content for the epidermis and blood content and oxygen saturation for the dermis. The scattering coefficient and refractive index of each layer were found in the literature. Diffuse reflectance spectra between 490 and 620 nm were generated using Monte Carlo simulations for a wide range of melanosome volume fraction, epidermal thickness, blood volume, and oxygen saturation. Then, an inverse method was developed to retrieve these physiologically meaningful parameters from the simulated diffuse reflectance spectra of skin. A previously developed accurate and efficient semiempirical model for diffuse reflectance of two layered media was used instead of time-consuming Monte Carlo simulations. All parameters could be estimated with relative root-mean-squared error of less than 5% for (i) melanosome volume fraction ranging from 1% to 8%, (ii) epidermal thickness from 20 to 150 mum, (iii) oxygen saturation from 25% to 100%, (iv) blood volume from 1.2% to 10%, and (v) tissue scattering coefficient typical of human skin in the visible part of the spectrum. A similar approach could be extended to other two-layer absorbing and scattering systems.


Assuntos
Melaninas/análise , Pele/irrigação sanguínea , Pele/química , Espectrofotometria/métodos , Epiderme/anatomia & histologia , Humanos , Modelos Biológicos , Método de Monte Carlo , Fenômenos Ópticos , Oxigênio/sangue , Espalhamento de Radiação , Pele/anatomia & histologia , Espectrofotometria/estatística & dados numéricos
17.
J Phys Chem Lett ; 11(9): 3731-3737, 2020 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-32302146

RESUMO

This work investigates the effect of wall thickness on the thermal conductivity of mesoporous silica materials made from different precursors. Sol-gel- and nanoparticle-based mesoporous silica films were synthesized by evaporation-induced self-assembly using either tetraethyl orthosilicate or premade silica nanoparticles. Since wall thickness and pore size are correlated, a variety of polymer templates were used to achieve pore sizes ranging from 3-23 nm for sol-gel-based materials and 10-70 nm for nanoparticle-based materials. We found that the type of nanoscale precursor determines how changing the wall thickness affects the resulting thermal conductivity. The data indicate that the thermal conductivity of sol-gel-derived porous silica decreased with decreasing wall thickness, while for nanoparticle-based mesoporous silica, the wall thickness had little effect on the thermal conductivity. This work expands our understanding of heat transfer at the nanoscale and opens opportunities for tailoring the thermal conductivity of nanostructured materials by means other than porosity and composition.

18.
ChemSusChem ; 13(5): 1013-1026, 2020 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-31808623

RESUMO

This study aims to investigate the effect of the potential window on heat generation in carbon-based electrical double layer capacitors (EDLCs) with ionic-liquid (IL)-based electrolytes using in operando calorimetry. The EDLCs consisted of two identical activated-carbon electrodes with either neat 1-butyl-1-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide ([Pyr14 ][TFSI]) electrolyte or 1.0 m [Pyr14 ][TFSI] in propylene carbonate (PC) as electrolyte. The instantaneous heat generation rate at each electrode was measured under galvanostatic cycling for different potential windows ranging from 1 to 4 V. First, the heat generation rates at the positive and negative electrodes differed significantly in neat IL owing to the differences in the ion sizes and diffusion coefficients. However, these differences were minimized when the IL was diluted in PC. Second, for EDLC in neat [Pyr14 ][TFSI] at high potential window (4 V), a pronounced endothermic peak was observed at the beginning of the charging step at the positive electrode owing to TFSI- intercalation in the activated carbon. On the other hand, for EDLC in 1.0 m [Pyr14 ][TFSI] in PC at potential window above 3 V, an endothermic peak was observed only at the negative electrode owing to the decomposition of PC. Third, for both neat and diluted [Pyr14 ][TFSI] electrolytes, the irreversible heat generation rate increased with increasing potential window and exceeded Joule heating. This was attributed to the effect of potential-dependent charge redistribution resistance. A further increase in the irreversible heat generation rate was observed for the largest potential windows owing to the degradation of the PC solvent. Finally, for both types of electrolyte, the reversible heat generation rate increased with increasing potential window because of the increase in the amount of ion adsorbed/desorbed at the electrode/electrolyte interface.

19.
Appl Opt ; 48(35): 6670-83, 2009 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-20011007

RESUMO

We present computationally efficient and accurate semiempirical models of light transfer suitable for real-time diffuse reflectance spectroscopy. The models predict the diffuse reflectance of both (i) semi-infinite homogeneous and (ii) two-layer media exposed to normal and collimated light. The two-layer medium consisted of a plane-parallel slab of finite thickness over a semi-infinite layer with identical index of refraction but different absorption and scattering properties. The model accounted for absorption and anisotropic scattering, as well as for internal reflection at the medium/air interface. All media were assumed to be nonemitting, strongly forward scattering, with indices of refraction between 1.00 and 1.44 and transport single-scattering albedos between 0.50 and 0.99. First, simple analytical expressions for the diffuse reflectance of the semi-infinite and two-layer media considered were derived using the two-flux approximation. Then, parameters appearing in the analytical expression previously derived were instead fitted to match results from more accurate Monte Carlo simulations. A single semiempirical parameter was sufficient to relate the diffuse reflectance to the radiative properties and thickness of the semi-infinite and two-layer media. The present model can be used for a wide range of applications including noninvasive diagnosis of biological tissue.


Assuntos
Luz , Modelos Teóricos , Óptica e Fotônica , Espalhamento de Radiação , Absorção , Anisotropia
20.
Nat Nanotechnol ; 14(11): 1048-1055, 2019 11.
Artigo em Inglês | MEDLINE | ID: mdl-31686005

RESUMO

Many living organisms track light sources and halt their movement when alignment is achieved. This phenomenon, known as phototropism, occurs, for example, when plants self-orient to face the sun throughout the day. Although many artificial smart materials exhibit non-directional, nastic behaviour in response to an external stimulus, no synthetic material can intrinsically detect and accurately track the direction of the stimulus, that is, exhibit tropistic behaviour. Here we report an artificial phototropic system based on nanostructured stimuli-responsive polymers that can aim and align to the incident light direction in the three-dimensions over a broad temperature range. Such adaptive reconfiguration is realized through a built-in feedback loop rooted in the photothermal and mechanical properties of the material. This system is termed a sunflower-like biomimetic omnidirectional tracker (SunBOT). We show that an array of SunBOTs can, in principle, be used in solar vapour generation devices, as it achieves up to a 400% solar energy-harvesting enhancement over non-tropistic materials at oblique illumination angles. The principle behind our SunBOTs is universal and can be extended to many responsive materials and a broad range of stimuli.

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