UNIVERSIDAD NACIONAL AUTONOMA DE MEXICO FACULTAD DE QUIMICA ALUMNOS: Coquet Dvila Manuel Benito Estrada Martnez Daniel Hernndez

dez Ventura Cristina Sanchez Miaur Fernando MATERIA: Electroqumica PROFESORA: Dr. Martha Aguilar Martnez TRABAJO: Dispositivos electrocrmicos duales basados en polmeros conductores. Fecha 29 de Abril del 2013

Por medio de investigacin durante la ltima dcada se ha llegado a la creacin de distintos materiales inteligentes y adaptivos para regular la cantidad de luz y de energa que fluye a travs de fachadas de vidrios. Estas tecnologas inteligentes regularmente se aprovechan de los siguientes comportamientos del material: termotrpicos, gasotrpicos y electrotrpicos. El comportamiento termotrpico es una tecnologa pasiva que responde a cambios de temperatura en el medio ambiente y se puede utilizar para controlar la emisin infrarroja y la transmitancia del vidrio, de manera similar al vidrio termocrmico. Los materiales termotrpicos tambin tienen la habilidad de cambiar la conductividad trmica del vidrio al igual que sus valores de transmitancia, lo que lleva a una mayor posibilidad de ahorro energtico. Sin embargo, el material termotrpico solo cambia de transmisivo a reflectivo a una temperatura especfica, la cual debe ajustarse dentro de una zona de confort para la gente para tener aplicaciones arquitectnicas reales. Actualmente, la mayora de estos materiales no han alcanzado esta zona de temperaturas y se encuentran en etapa de investigacin y no de aplicacin. Una desventaja general de los sistemas pasivos de control es que su productividad solo se puede optimizar de acuerdo a un slo factor (en este caso la absorcin de calor solar), y no se puede controlar de manera manual para poder tomar en cuenta otras variables como los niveles de luz visible. El comportamiento gasotrpico se relaciona al cambio en propiedades pticas del material causado por una reaccin qumica entre una capa especial depositada en el vidrio y un gas alimentado a la cavidad entre los dos paneles de vidrio. Las ventaja principal del vidrio gasotrpico es que puede retener propiedades de alta transmisin en el estado transparente y no reactivo y adems tambin posee una habilidad de cambio rpido entre estados; le toma 20 segundos para cambiar del estado transparente al colorido, y menos de un minuto para regresar al estado transparente. Los problemas principales surgen a partir de la complejidad del sistema de inyeccin del gas y el acumulamiento de agua cuando tomos de hidrgeno se aaden para el proceso qumico. En este momento la tecnologa gasotrpica y gasocrmica no es econmicamente viable pero se investiga extensamente para alcanzar comerciabilidad en un futuro.

El comportamiento electrpico se relaciona al electrocromismo y en sistemas de vidrio inteligente se encuentran tres aparatos principales: tecnologa de cristal lquido, aparatos electrocrmicos y aparatos de partculas supendidas.
El electrocromismo es un proceso por el cual un material cambia sus propiedades electropticas mediante la aplicacin de un potencial elctrico a travs del material. Tpicamente, estos cambios electropticos ocurren en la regin visible del espectro y con un cambio de color en el material dado un cambio en el potencial. Tambin se han explotado otras propiedades electropticas como lo son la opacidad, la reflectividad y la cantidad de luz que pasa para regular la temperatura y el ahorro energtico. Los polmeros conjugados son una clase de materiales electrocrmicos muy interesantes por su habilidad de exihibir distitntos tonos de colores, su sintonizabilidad de colores, sus altos contrastes pticos, su rpida velocidad de cambio y su procesabilidad.

Dado que las propiedades pticas intrnsicas del polmero estn determinadas por la banda de absorcin de polmero y su absorcin mxima, la sintonizacin de colores se puede realizar al modificar estos valores. De manera ms especfica, esto se logra mediante la ingeniera molecular al modificar la estructura del polmero. Un ejempo se muestra en la imagen anexa para una serie de polmeros electrocrmicos solubles spray-cast en una capa de ITO-vidrio en sus estados neutros y dopados.

Polmeros electrocrmicos Cathodically coloring spray-cast en ITO-coated glass

Durante la oxidacin del polmero, se crean estados de banda media con transiciones electrnicas ocurriendo ahora a niveles de energa ms bajos. En algunos de los casos, como el que presenta el politiofeno, el polmero tiene color en ambos estados, el neutro y el oxidado. En el caso de los poli(3,4-alquenodioxitiofenos), el polmero adquiere un color en el estado neutro y se vuelve transmisivo en el estado oxidado con las transiciones electrnicas ahora ocurriendo cerca del espectro infrarrojo (tambin llamados cathodically coloring polymers). De manera anloga, polmeros como los poli(3,4-alquenodioxipirrol)es exhiben su absorcin en la regin UV con el polmero neutro siendo transmisivo con una absorcin incrementando en el visible dada oxidacin (anodically coloring polymers). Esto se demuestra con la progresin espectroelectroqumica del poli(3,4-eltilendioxitiofeno) (PEDOT) cambiando de un color azul oscuro en un estado neutro a un altamente transmisivo azul cielo cuando se oxida.

Absorcin espectroelectroqumica del PEDOT. Las flechas indican la progresin del espectro de absorcin al incrementar el potencial aplicado

Los aparatos electrocrmicos transforman propiedades de transmisin de luz en respuesta al voltaje y as permiten controlar la cantidad de luz y de calor que pasa a travs. Son probablemente la tecnologa ms popular y compleja de acristalamiento por medio de materiales inteligentes. El aparato consiste de una pelcula electrocrmica delgada y slida que se aplasta entre dos capas de vidrio. Al pasar una corriente con un voltaje pequeo a travs de la pequea pelcula, la capa electrocrmica se activa y cambia de un color claro a uno oscuro. Con este cambio de color el vidrio controla sus propiedades de transmisin ptica. El vidrio electrocrmico puede controlar la radiacin solar al absorber el calor en su estado oscuro, aunque esto puede calentar el vidrio. Una ventaja es que el voltaje pequeo solo se debe aplicar hasta que se de la coloracin y el material adquiere memoria del color y tambin la transmisin de radiacin hasta por 48 horas. La corriente elctrica se puede administrar de manera manual o por sensores activos que responden a la luz externa. El oscuramiento del vidrio puede reducir la transmisin solar, y cuando hay poca luzel vidrio se puede aclarecer, reduciendo la necesidad de usar luz artificial. El tiempo requerido para generar el cambio de color toma alrededor de 30 minutos para una ventana de alrededor de 2.4 m2. La durabilidad del acristalamiento es otro problema ya que actualmente tienen una vida de alrededor de 10-15 aos ya que tienen que soportar ciclos repetidos de cambio de estado. En las ventanas electrocrmicas, el material electrocrmico cambia su opacidad; cambia de un estado colorido y translcido (generalmente azul) a un estado transparente. Para cambiar su opacidad se requiere aplicar cierta cantidad de electricidad, pero una vez que se da el cambio, no se necesita electricidad para mantener el tono o sombra alcanzado. El oscuramiento ocurre desde las paredes hacia adentro y es un proceso muy lento; puede

tomar de muchos segundos a varios minutos de acuerdo al tamao de la ventana. El vidrio electrocrmico muestra visibilidad an en el estado oscuro y as mantiene un contacto visible con el medio ambiente desde afuera y adentro. Se ha utilizado para aplicaciones a escala pequea como espejos retrovisores. La tecnologa electrocrmica tambin se utiliza para necesidades de uso interno como proteccin de objetos en museos, marcos de fotos para evitar daos de los rayos UV y de regiones visibles de luz artificial y para el ahorro energtico. Avances recientes en materiales electrocrmicos relacionados a hbridos de metales de transicin han llevado al desarrollo de hbridos reflectivos. Estos materiales se convierten en reflectores en vez de absorber luz y cambian entre un estado transparente y un estado similiar a un espejo. BIBILIOGRAFIA Carrillo Ramiro, Isabel, Polmeros conductores sntesis y caracterizacin electroqumica, estructura y morfologa, Universidad complutense de Madrid, Espaa, 1996, 243 pp. Fernndez Otero, Toribio, Los polmeros conductores como materiales biommticos, Universidad del Pas Vasco, San Sebastian, 1997, 8 pp. Fernndez Otero, Toribio, Polmeros conductores: sntesis, propiedades y aplicaciones electroqumicas, Revista iberoamericana de polmeros, Espaa, 2003, 32 pp. Padilla Martnez, Javier, Polmeros conductores: su papel en un desarrollo energtico sostenible, Barcelona, Ed. Revert, 2010, 166 pp. Padilla Martnez, Javier, Caracterizacin y optimizacin electroqumica de polmeros conductores, Universidad Politcnica de Cartagena, Espaa, 203 pp. https://ww2.chemistry.gatech.edu/reynolds/research/electrochromic_polymers http://www.smartglassinternational.com/wp-content/uploads/2011/01/CambridgeUniversity-SPD-SmartGlass-Report.pdf

Recent advancements in modified porous nano-crystalline films have enabled the creation of electrochromic display. The single substrate display structure consists of several stacked porous layers printed on top of each other on a substrate modified with a transparent conductor (such as ITO or PEDOT:PSS). Each printed layer has a specific set of functions. A working electrode consists of a positive porous semiconductor (say Titanium Dioxide, TiO2) with adsorbed chromogens (different chromogens for different colors). These chromogens change color by reduction or oxidation. A passivator is used as the negative of the image to improve electrical performance. The

insulator layer serves the purpose of increasing the contrast ratio and separating the working electrode electrically from the counter electrode. The counter electrode provides a high capacitance to counterbalances the charge inserted/extracted on the SEG electrode (and maintain overall device charge neutrality). Carbon is an example of charge reservoir film. A conducting carbon layer is typically used as the conductive back contact for the counter electrode. In the last printing step, the porous monolith structure is overprinted with a liquid or polymer-gel electrolyte, dried, and then may be incorporated into various encapsulation or enclosures, depending on the application requirements. Displays are very thin, typically 30 micrometer, or about 1/3 of a human hair. The device can be switched on by applying an electrical potential to the transparent conducting substrate relative to the conductive carbon layer. This causes a reduction of viologen molecules (coloration) to occur inside the working electrode. By reversing the applied potential or providing a discharge path, the device bleaches. A unique feature of the electrochromic monolith is the relatively low voltage (around 1 Volt) needed to color or bleach the viologens. This can be explained by the small over- potentials needed to drive the electrochemical reduction of the surface adsorbed viologens/chromogens.

Suspended particle devices [edit]

In suspended particle devices (SPDs), a thin film laminate of rod-like particles suspended in a fluid is placed between two glass or plastic layers, or attached to one layer. When no voltage is applied, the suspended particles are arranged in random orientations and tend to absorb light, so that the glass panel looks dark (or opaque), blue or, in more recent developments, grey or black colour. When voltage is applied, the suspended particles align and let light pass. SPDs can be manually or automatically tuned to precisely control the amount of light, glare and heat passing through, reducing the need for air conditioning during the summer months and heating during winter. Other advantages include reduction of buildings' carbon emissions and the elimination of a need for expensive window dressings.

Polymer dispersed liquid crystal devices [edit]

In polymer dispersed liquid crystal devices (PDLCs), liquid crystals are dissolved or dispersed into a liquid polymer followed by solidification or curing of the polymer. During the change of the polymer from a liquid to solid, the liquid crystals become incompatible with the solid polymer and form droplets throughout the solid polymer. The curing conditions affect the size of the droplets that in turn affect the final operating properties of the "smart window". Typically, the liquid mix of polymer and liquid crystals is placed between two layers of glass or plastic that include a thin layer of a

transparent, conductive material followed by curing of the polymer, thereby forming the basic sandwich structure of the smart window. This structure is in effect a capacitor. Electrodes from a power supply are attached to the transparent electrodes. With no applied voltage, the liquid crystals are randomly arranged in the droplets, resulting in scattering of light as it passes through the smart window assembly. This results in the translucent, "milky white" appearance. When a voltage is applied to the electrodes, the electric field formed between the two transparent electrodes on the glass causes the liquid crystals to align, allowing light to pass through the droplets with very little scattering and resulting in a transparent state. The degree of transparency can be controlled by the applied voltage. This is possible because at lower voltages, only a few of the liquid crystals align completely in the electric field, so only a small portion of the light passes through while most of the light is scattered. As the voltage is increased, fewer liquid crystals remain out of alignment, resulting in less light being scattered. It is also possible to control the amount of light and heat passing through, when tints and special inner layers are used. It is also possible to create fire-rated and anti X-Ray versions for use in special applications. Most of the devices offered today operate in on or off states only, even though the technology to provide for variable levels of transparency is easily applied. This technology has been used in interior and exterior settings for privacy control (for example conference rooms, intensive-care areas, bathroom/shower doors) and as a temporary projection screen.

Micro-blinds [edit]

Scanning Electron Microscope (SEM) image of Micro-blinds

Micro-blindscurrently under development at the National Research Council (Canada)[1][2]control the amount of light passing through in response to applied voltage. Micro-blinds are composed of rolled thin metal blinds on glass. They are very small and thus practically invisible to the eye. The metal layer is deposited by magnetron sputtering and patterned by laser or lithography process. The glass substrate includes a thin layer of a transparent conductive oxide (TCO) layer. A thin insulator is deposited between the rolled metal layer and the TCO layer for electrical disconnection. With no applied voltage, the micro-blinds are rolled and let light pass through. When there is a potential difference between the rolled metal layer and the transparent conductive layer, the electric field formed between the two electrodes causes the rolled micro-blinds to stretch out and

thus block light. The micro-blinds have several advantages including switching speed (milliseconds), UV durability, customized appearance and transmission. Theoretically, the blinds are simple and cost-effective to fabricate.[1][2] A video available on YouTube [3] describes briefly the microblinds.

Mechanical smart windows [edit]

A low cost alternative to high-tech intelligent windows is composed of two retro reflective panels mounted back-to-back with a narrow gap in between. When a liquid with the same refractive index as that of the panels is pumped into the cavity between them, the glass becomes transparent. When the liquid is pumped out, the glass turns retro reflective again. An example of this kind of window is the Norwegian brand, Sunvalve

Related areas of technology [edit]

The expression smart glass can be interpreted in a wider sense to include also glazings that change light transmission properties in response to an environmental signal such as light or temperature. Different types of glazing can show a variety of chromic phenomena, that is, based on photochemical effects the glazing changes its light transmission properties in response to an environmental signal such as light (photochromism), temperature (thermochromism), or voltage (electrochromism). Liquid crystals, when they are in a thermotropic state, can change light transmission properties in response to temperature. Recent advances in electrochromic materials have led to the discovery that transition metal hydride electrochromics create a reflective face instead of an absorbent face. These materials have the same idea, but go about the problem in a different way by switching between a transparent state when they are off to a reflective state when a voltage is applied. Switchable mirrors were originally developed by Tom Richardson and Jonathan Slack of Berkeley Labs Environmental Energy Technologies Division. They used rare earth metals and created the first metal-hydride switchable mirrors. Low emittance coatings reject unwanted thermal heat due to solar infrared21. These mirrors have become common place in cars rearview mirrors in order to block the glare of following vehicles. An optically absorbing electrochromic color reduces the reflection intensity. These mirrors must be fully transformed to a reflective state as muted reflection must persist in the darkened state. Originally a metal, they are converted

into a transparent hydride by injecting hydrogen in a gas or liquid phase. It then switches to a reflective state. Various metals have been investigated. Thin Mg-Ni films have low visible transmittance and are reflective. When they are exposed to H2 gas or reduced by an alkaline electrolyte, they become transparent. This transition is attributed to the formation of magnesium nickel hydride, Mg2NiH4. Films were created by cosputtering from separate targets of Ni and Mg to facilitate variations in composition. Single-target d.c. magnetron sputtering could be used eventually which would be relatively simple compared to deposition of electrochromic oxides, making them more affordable. Lawrence Berkeley National Laboratory determined that new transition metals were cheaper and less reactive, but contained the same qualities, thus further reducing the cost. Tungsten-doped Vanadium dioxide VO2 coating reflects infrared light when the temperature rises over 29 degrees Celsius, to block out sunlight transmission through windows at high ambient temperatures. These types of glazings cannot be controlled manually. In contrast, all electrically switched smart windows can be made to automatically adapt their light transmission properties in response to temperature or brightness by integration with a thermometer or photosensor, respectively The topic of smart windows in a further sense includes LED Embedded Films which may be switched on at reduced light intensity. The process of laminating these LED embedded films between glass will allow the production of Transparent LED embedded glasses. As most glass companies are not skilled in mounting LEDs (Light Emitting Diodes) onto metallized glass, the LEDs are located on a separate transparent conductive polymeric interlayer[4] that may be laminated by any glass lamination unit. Production technologies Smart glass is produced by means of lamination of two or more glass or polycarbonate sheets.[5].

LC Technology Liquid crystal glazing is made up of two sheets of glass surrounding a liquid crystal film. With the application of an electric field, the orientation of these liquid crystal chains can be altered and therefore the optical transmission of the glass also. When no voltage is applied the molecules are randomly scattered and visual light is diffused in multiple directions, giving a translucent opal white effect. When a voltage is applied the molecules align with the electric field and light can pass through unobstructed. LC power consumption is low in general less than 5 W/m2 [7] and the transition from opaque to clear is immediate. However LC technology is not able to reduce the amount of radiation transmission from the sun very effectively. LC glass affects the way light is

transferred but does not alter the quantity of radiation, and thus heat flow through glass, making it unsatisfactory for energy saving purposes. The use of LC glass is currently popular for internal architectural designs, such as privacy partitions, though due to many limitations does not have a foreseeable future as an external building faade. [7] SPD technology SPD is a film based technology, with a uniform response throughout the film. The film contains rod-like particles suspended in billions of liquid droplets distributed across the film. When the film has no applied voltage the particles are in random positions and block light transmission, appearing as a dark blue tint. When a voltage is then applied, the particles align and light is allowed to go through. The change in tint is instant and a user advantage to this technology is that the voltage can be varied to give a different level of tint and therefore the transmission properties can be changed to suit any particular external environment. [7] SPD windows hold energy saving potential for the device uses solid radiation-absorbing particles in the liquid suspension. Precise optical properties depend on the thickness of the suspension film as well as the concentration of particles within [6]. Solar radiation and visible light transmittance is reduced with the application of a voltage, which in turn reduces the heat flow into the internal environment. SPD windows allow clear sight through the glass even while fully switched on and in a state of minimum transmission, which holds a visual advantage over other glazing technologies that turn the glass cloudy. The current downside of this technology is the cost. As its a very recent development, it is still in the early stages of demand, with the patent owner controlling prices. With sufficient marketing and its energy saving advantages made known then cost will come down as unit demand increases.

2.4 SPD Technology in Detail As this project is investigating the performance of SPD SmartGlass the following section looks at the theory and advantages of this material in more detail. Figures and technical data are provided by SmartGlass Internationals Overview of their SPD glass [13] SPD is a film-based technology, as explained earlier, which comprises of billions of rotating particles inside a dual-layer plastic film. Figure2.b shows the mechanism that occurs as a voltage is applied to the conductive coatings surrounding the particle emulsion. This set-up is similar to a basic parallel-plate capacitor, which has a uniform electric field. This results in a uniform response throughout the SPD film when switching from clear to tinted, which is not possible with most electrochromic devices. When SPD is tinted it holds a bluish tint, which reduces to clear when switched on. This level of tint can be

controlled by the magnitude of voltage applied to the glass SPD glass requires an ac voltage to function, as a dc voltage will cause the polarized particles to migrate and cluster in the film, resulting in a gradual darkening Figure.2b diagram of SPD technology Technical data for SPD SmartGlass supplied by SmartGlass International can be found below in Table 2 Table 2 technical data of SPD glass from [13] This configuration is recommended by SmartGlass Int. to achieve the highest possible performance. This data also shows the high level of UV blocking by SPD glass, in both the ON and OFF state. SPD SmartGlass UValue* RValue* STC* OITC* UV Blocking On (Clear) 0.24 4.17 34 26 >99.5% Off (Dark) 0.24 4.17 34 26 >99.5%
Smart Building Envelopes Part IIB Project Mark Beevor Page 15

Main advantages of SPD windows; Accurate lighting control, while maintaining an optical view through the window. Even with the bluish tint, it is still possible to see through the glass. Figure.2c below shows the variation of window colour in the ON/OFF state The high durability and long life expected for smart glass technology. Testing has occurred for over 100,000 cycles without an degeneration of performance Reduced glare in working environments that will cause uncomfortable conditions, disruption to computer operation, and possible eye strain A wide working temperature from -30C to +90C so suitable for glass faades in numerous climates. The temperature of glass in very sunny Figure.2c different tint of SPD windows locations can reach extremely high levels so this upper bound is very critical.

 Energy saving due to the reduced cooling and lighting costs. SPD windows are able to reduce the solar heat gain into an office and therefore create a more stable and cooler internal environment. The ability to control light levels also removes the need to have blinds and therefore the use of artificial lighting throughout the day.