text:
LSU Junior
40: 4.45
Has a tall, long frame with very good athleticism. Has good hips and turns and runs with receivers very well. Can mirror them, and has good burst out of his breaks. Has quick feet and plays balanced on his drops. Has excellent ball skills and consistently high points the ball in the air. Does a good job getting inside position on the deep patterns and breaking up passes. Will jump the crossing routes due to his burst and make plays there. Is very good in press coverage as he does a good job getting the jam and knocking the receiver off his route. WIlling in run support, stepping up and delivering a hit off the edge. Will wrap up at times in the open field. Has nice closing burst in pursuit to chop the legs of a big tight end to make the stop. Works well as a kickoff returner due to good straight-line speed and acceleration to hit the seam quickly.
Has sloopy technique at times. Doesn't sit in his backpedal, which can limit his burst upfield at times and prevent him from driving on underneath throws. Not very effective in off coverage because he doesn't take good angles to the ball after giving up the underneath catch. Can play flat-footed and unbalanced at times, trusting too much in his athleticism to mirror the receiver. Gets a bit handsy at times when running downfield with receivers, and can draw some penalties. Is not particularly adept against the run, as he doesn't do a good job wrapping up. Needs to do a better job breaking down at the point of attack, and not a guy you can trust to make stops in the open field. Doesn't have great awareness vs. the run, as he can get caught out of position and lose outside contain, especially when he's working off the line of scrimmage. Has difficulty getting off blocks at times when going against the screen. Dances a bit too much at times as a kickoff returner and doesn't have great burst out of cuts, because he tends to chop his feet.
Claiborne is a top athlete with a tall, long frame that is rare in corners. He is a very good press corner and shines there, but is not nearly as adept when he's working off. He has the potential to be a very good matchup corner in a press-heavy scheme, and you can leave him on an island against a top wideout. He's not quite the premier athlete that Patrick Peterson was, and he's still a little unpolished as a corner. Part of that is because he was mainly quarterback in high school, came to LSU to play receiver, but moved to corner in his freshman fall camp. Claiborne has the upside you want in a corner, and in the right scheme he can definitely be a player that can slant the field. He's only just begun to scratch the surface of his potential.
(9/3) vs. Oregon: 1 missed tackle; 3 targets, 2 rec., 24 yds, 12.0 avg, 21 YAC, 0 TDs
(9/15) at Mississippi St: 1 missed tackle, 1 key blocked; 4 tgt., 0 rec., 0 yds, 1 INT, 1 PD
(11/5) at Alabama: 3 tgt., 0 rec., 0 yds, 1 INT, 1 PD
(12/3) vs. Georgia: 5 tgt., 3 rec., 60 yds, 20.0 avg, 19 YAC,; 1 INT, 1 PD; 1 penalty (def. holding)
(1/9) vs. Alabama: 0 tgt., 0 rec., 0 yds
2011: 14 GP/14 GS, 51 tackles, 1.0 TFLs, 0.0 sacks, 6 INTs, 6 PD, 0 FF, 0 FR; 22 KOR, 25.1 avg, 1 TDS
2010: 12/12-37-1.0-0.0-5-6-0-1; 2-28.5-0
2009: 7/0-7-0.0-0.0-0-0-0-0
- missed 1 game in 2010 due to a concussion
Claiborne can be one of the premier corners in the league if he goes to the right scheme. A press heavy scheme that will put him on an island against a top wideout, and he could be a very good player. If you want him to play off coverage, then he's going to be a lot less effective because he's just not great there. I think in the right scheme, he can value similar to Nnamdi Asomugha in Oakland, but it wouldn't surprise me if his NFL career mirrors that of Antonio Cromartie a bit. I think he can be prone to get beat from time to time, but he has the ability that if he develops, he can slant the field like Asomugha did. Quarterbacks aren't going to want to challenge him because he can make them pay. He's not a guy that I think is going to get a ton of interceptions when all is said and done because like Asomugha teams will try to avoid him. Early in his career, he'll probably be able to rack up higher interception totals because teams will be less willing to avoid him, which should give him more opportunities. He has to improve though, and polish up his footwork and technique a bit more. I think he can and will, but he's not there yet. So I don't expect him to come into the league right away and be a top corner. But it shouldn't take him more than a year or two to start to live up to his potential and be a No. 1 corner. Unlike Peterson, he's not a versaile guy that can play multiple roles in multiple schemes. He's a very scheme-specific player that within that scheme he can be a very good player. Outside that scheme, he's more likely to be only an above average starter. He has the ability and potential to improve in the areas where he's currently weak in, and a player with his athleticism isn't ever going to be poor at anything. But if he goes to a team that wants him to play off zone or off man, it's going to take him a lot longer before he impacts as a top-tier corner, if ever.
Nnamdi Asomugha, Eagles.
Claiborne would be a very good fit in Mike Nolan's scheme which prefers bigger press corners, That's because Claiborne can be left on an island, and his ability to jam receivers gives those blitzes a lot more time to get to the quarterback, and also allows the coaches to mix up their blitzes more because now safeties can be brought into the fray. He played predominantly on the right side at LSU, and would be a good fit to work behind Robinson for a year. But his upside and ability would almost certainly push Robinson off the roster. While Claiborne could get looks in the slot as a rookie, he probably would not thrive in that role as the nickel guy between Robinson and Grimes. The Falcons would probably be better off moving Grimes to the slot and having Claiborne play on the outside in nickel situations.
For a team that will use him in the right scheme, Claiborne offers Top 10 potential. For a team that wants to be a bit more multiple with their schemes, he's better value in the middle to later portion of the first round.
1-pathetic, 2-poor, 3-weak, 4-below average, 5-average, 6-above average, 7-good, 8-very good, 9-excellent, 10-elite
Speed: 8.5
Man Coverage: 8.0
Zone Coverage: 6.0
Tackling: 5.0
Ball Skills: 9.0
Morris Claiborne, CB, LSU
Scouting reports of the cornerbacks in the 2012 Draft.
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House says he'll play
Posted by Marc J. Spears, Globe Staff March 17, 2009 02:55 PM
CHICAGO -- Celtics guard Eddie House said today that other than a bruise, his left ankle is fine and he will play tonight against the Bulls.
House injured the ankle during Sunday's loss to Milwaukee.
Paul Pierce is hampered by a sore throat, but will play.
News, analysis and commentary from the following Boston Globe and Boston.com writers:
- Gary Washburn, NBA writer
- Baxter Holmes, Celtics beat writer
- Gary Dzen, Boston.com senior sports producer
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This invention discloses pre-formed electrochromic films that are used in assembly of electrochromic devices. These films are laminated to conductive substrates to form the electrochromic devices. The invention also discloses optical characteristics of the substrates for imparting durability to the electrochromic devices from solar radiation.
1. An electrochromic device formed by assembling a pair of substrates having conductive layers with a preformed multi layer film formed independently of the conductively coated substrate, wherein the device is assembled with the conductive layers of the substrates facing inwards and sandwiching the pre-formed multilayer solid film wherein the said preformed multi layer film comprises at least two layers with different compositions, and at least one of these layers having electrochromic properties and at least one layer having electrolytic properties.
2. An electrochromic device formed as in
3. An electrochromic device formed as in
4. An electrochromic device formed as in
5. An electrochromic device formed as in
6. An electrochromic device formed as in
7. An electrochromic device formed by assembling a pair of substrates having conductive coatings with a preformed multi layer film formed independently of the conductively coated substrate, wherein the device is assembled with the conductive coatings of the substrates facing inwards and sandwiching the pre-formed multilayer solid film wherein the said preformed multilayer film comprises at least three layers with different compositions, and at least one of these layers having anodic properties, another one of these layers having electrolytic properties and another one of these layers having cathodic properties.
8. An electrochromic device formed by assembling a pair of substrates having conductive coatings with at least two preformed film layers formed independently of the conductively coated substrate, wherein the device is assembled with the conductive coatings of the substrates facing inwards and sandwiching the pre-formed layers with different compositions, and at least one of the preformed film layers having electrochromic properties and at least one layer having electrolytic properties.
9. An electrochromic device formed by assembling a pair of substrates having conductive coatings with preformed film layers formed independently of the conductively coated substrate, wherein the device is assembled with the conductive coatings of the substrates facing inwards and sandwiching at least three pre-formed layers with different compositions, and at least one of these pre-formed layers having anodic properties, another one of these pre-formed layers having electrolytic properties and another one of these pre-formed layers having cathodic properties.
10. A variable reflectivity automotive mirror formed by assembling a pair of bent substrates with a preformed multi layer film formed independently of the substrates, wherein the device is assembled with the substrates sandwiching the preformed multi layer film, and at least one of these pre-formed layers in the said film comprises a variable light modulating medium.
This application is related to and claims priority from U.S. Provisional application 60/936,065 filed on Jun. 18, 2007 and U.S. provisional patent application 60/998,758 filed on Oct. 13, 2007, both of which are incorporated by reference herein.
The present invention relates to forming electrochromic (EC) devices particularly usable for window applications for architectural, transportation, display and other applications.
The present invention relates to electrochromic devices for varying the transmittance or reflection to light, such as windows for buildings, transportation (e.g., motor vehicles, buses, trains, planes, boats). Devices from this invention may also be used for displays (including indicators), and rear-view mirrors for vehicles, motor cycles, etc.
Reversibly variable electrochromic devices are known in the art. In such devices, the intensity of light (e.g., visible, infrared, ultraviolet or other distinct or overlapping electromagnetic radiation) is modulated by passing the light through an electrochromic medium. The electrochromic medium is disposed between two conductive electrodes, at least one of which is typically transparent, and causes the medium to undergo reversible electrochemical reactions when potential differences are applied across them. The electrochromic devices may be divided in two distinct types. In one, a stack of thin films is used on a single substrate that comprises of all the transparent conductors, electrolyte and other electrode layers. Examples of these devices are in US patent applications 2007/0097481 and 2007/0103761. In the other type of EC devices two substrates are used, which have pre-deposited layers of conductors and may also have other pre-deposited redox electrode layers in addition to the conductors. These substrates are put together as a sandwich where the center is a liquid or a polymeric solid electrolyte. Examples are described in U.S. Pat. Nos. 3,280,701; 4,712,879; 4,902,108; 5,007,718; 6,178,034 and 6,266,177. Electrochromic materials in this invention are those that change color when oxidized or reduced.
For EC windows it is desired that the devices have good memory, this means once the window is colored or bleached, it remains in that optical state for a long period of time with minimum or no power, i.e., their power consumption is low to keep the desired optical state or one may be able to power the device intermittently without changing the transmission too much from the desired value. Such devices, with good memory, usually employ additional electrochromic and/or ion storage coatings on the substrates which are laminated with an ion conducting (or an electrolyte) layer as described in U.S. Pat. Nos. 6,266,177; 6,172,794 and US patent application 2006/0159610. In these devices, the added processing operations related to additional coatings deposition, their etching and reduction of at least one layer (if used) adds to the cost.
Devices with a sequence of thin coatings on a single substrate are also expensive to produce, particularly with increasing area. First, such all thin film stacks are sensitive to yield due to defects in thin coatings and, second, the deposition of layers by physical vapor deposition (PVD) is expensive as many of these layers are thick and are typically in the range of 300 to 1000 nm. Further, many of these devices need additional layers to reduce shorting and may also require additional processing steps for ion intercalation (e.g., see US patent application 2007/0097481).
To reduce cost of EC devices it is desirable to produce components using mass scale production methods. One method is to use a lamination process. This is a standard method where a polymeric sheet is laminated to a substrate. This method is well understood and is widely available. For example, laminated glass is available in a price range acceptable to end-customers for use in scatter (or shatter) resistant glass in climates where large wind loads are expected, and in automotive industry these windows reduce outside noise, and in case of windshields all cars in U.S. are required to only use laminated glass by the Federal Motor Vehicle Safety Standards. One way of implementing this procedure to manufacture EC devices cost effectively is to produce a solid laminating film with all the EC characteristics using mass processes such as extrusion and casting. The conductive substrates are being produced in large sizes and volumes for many other applications which may be used for these devices.
Glass with transparent conductive coatings, for example, fluorine doped tin oxide, is available from a variety of sources at a reasonable price (e.g., from Pilkington (Toledo, Ohio) as TEC 15, TEC 8). These and other conductors such as ITO and others are also available in large sizes due to the demands faced by flat panel display and solar cell industry on large coated substrates. For mirrors one may also use metal coatings on substrates as one of the conductive electrode layers. Particularly electrochromic rear-view mirrors for vehicles and windows for aircrafts and vehicles which are bent could be produced by laminating an electrolyte sheet between two appropriately bent substrates. It will be desirable to make solid EC devices using the lamination process without having to further coat the conductive substrates with any additional electrode layers.
In accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention provides materials and methods of forming cost-effective laminated EC devices. This includes composition and preparation of solid electrochromic polymeric sheets that are laminated to conductive substrates to form such laminated devices.
Another objective of the invention is the use of substrates and materials that block part of the visible radiation in order to enhance the durability of windows to solar radiation.
In EC devices, particularly used for large area windows and large displays, it is important that the devices have good memory. This allows devices to color uniformly and deeply without high charge consumption or a large voltage drop. Further, it also helps in reducing the energy consumed by such devices, particularly if these are supposed to reside in dark and transparent states for long periods of time. In the automotive industry, the power available to run the gadgets while the vehicle is parked is small, thus it is preferred that the desired state of the EC window selected by the user be maintained without consuming any significant power. It would be desirable to have the same for any type of transportation (buses, planes, boats, etc.) to not draw any power or low power to be able to shade the interiors from the Sun while parked for long periods. In addition, when the user commands a change in the window transmission, it should respond rapidly. For certain windows, to meet safety considerations it may be desirable that they self bleach upon the removal of power in a reasonable time.
Typically good memory in EC devices means to hold within 5% of any desired state of transmission without applying power preferably for a long period. For transportation the window temperature during normal operation may vary from −40� to about 85� C., and for architectural windows this variation is typically from about −40� to 60� C. This holding period at typical use temperature is preferably from a few minutes at the use temperature, to several hours or more depending on the application. For automotive glazing applications at room temperature, this should preferably exceed 2 hours. Usually, the memory period decreases with increasing temperature. Thus the ability of the EC window to hold the desired transmission when evaluated at the upper limits of these temperature ranges may be shorter. The presence of memory allows one to design power supplies to hold the windows in desired transmission states for longer time by only providing a trickle charge which may also be derived from a solar cell. Another way to quantify the memory is by measuring the leakage current. The leakage current is measured as the steady state current while a voltage is applied to hold at the desired coloration level. Typically this current is measured in the deepest state of coloration specified for the operation of the device. This current changes with temperature and usually increases with increasing temperature. It should be measured at the upper use temperature, which for automotive glazing is 85� C. and building glazing is 60� C., and should be less than 2 μA/cm2 of the active EC area, or preferably less than 0.5 μA/cm2 and most preferably less than 0.05 μA/cm2. In terms of power, most EC devices switch completely in a range of 1 to 3V. One may specify this also in terms of power consumption which should be less than 5 μW/cm2, or preferably less than 1.2 μW/cm2 or most preferably less than 0.12 μW/cm2. A fast change from one optical state to the next is preferred which may range from a fraction of a second (for some displays) to a few minutes (less than 5 minutes for windows) for most applications. This change rate depends on the size of the window, and it decreases with increasing size while holding all other parameters constant. For self-bleach devices, the leakage current is higher. However, there is no clear value above which the device can be always called self-bleaching and below that value considered as having good memory, as it depends on the application. For windows one may use a leakage current in excess of 20 μA/cm2 as one that self-bleaches, or more preferably in excess of 100 μA/cm2 as being characterized as self bleaching window.
In prior art there are several examples where laminatable electrolytes were used to produce EC windows. Some of these are U.S. Pat. Nos. 6,361,709; 6,475,663; 6,767,624, 7,118,694; 6,995,891, 6,639,708; and US patent application 2006/0159610. All of these describe electrolyte compositions, electrolyte thicknesses, adhesion promotion to the coated substrates, methods of making, mechanical and ionic properties, processes to form EC devices and perimeter sealing of such devices. However, many of the issues identified in these patents such a compositions of electrolytes, processing methods and sealing are applicable to this invention as well, thus all of these publications are incorporated herein by reference. In the present invention, the EC layers are prepared by adding additional components to the electrolytes identified in the above inventions, and processed using similar lamination processes.
In this invention, a single pre-formed homogenous film of the electrolyte with EC characteristics, or a multiple layer pre-formed film may be used which in addition to the ion-conduction layer (traditional electrolyte layer in solid devices) also comprises of at least one additional redox layer, preferably two additional layers i.e., anodic and cathodic redox layers.
In prior art (references listed above), coatings were used to impart separate cathodic and anodic characteristics to window devices. Such coatings were deposited on the substrates, and then laminated with an ion conducting layer. In this invention such characteristics are provided into a pre-formed laminating film which has electrolytic characteristics and also distinct anodic and cathodic layers. In another set of prior art devices, the cathodic and anodic materials are mixed with the electrolyte (for example, see U.S. Pat. Nos. 4,902,108; 5,140,455, 6,241,916; 6,961,168) and filled as liquids into a pre-fabricated empty cavity with conductive coatings. These devices primarily yield self-erasing or self-bleaching characteristics, i.e. they automatically bleach in a short time after the removal of power (from a few seconds to a few minutes). In the present invention a single layer film is pre-formed with both electrolytic and EC characteristics which is then laminated to the conductive substrates. In both types of devices additional layers such as those that promote adhesion to the substrates or provide added functionality may be applied on to the surfaces of these films or on to the substrates before lamination. The important aspect of this invention is to understand the novelty that a film is pre-formed with both electrolytic and electrochromic functions which is then laminated with conductive substrates to yield an electrochromic device. In all cases this will be referred as pre-formed solid EC film that is further processed by laminating to the conductive substrates to form an EC device. The layers of the laminatable film described above may also be prepared separately and then bonded together as a solid film prior to laminating them to the substrates, or all of these discrete layers may be individually placed between the substrates and laminated together.
In the innovation described here, the laminatable solid EC film is fabricated in several ways. For memory devices, this film has multiple layers, preferably three layers, one anodic, one cathodic and in between these two layers is an electrolyte layer. At least one of the redox species used in this film, i.e., anodic or the cathodic species has to be electrochromic. It is desirable that the anodic and the cathodic layers also have high ion conductive properties. This composite film may be prepared in any fashion, but it is preferably prepared in a cost effective way in large quantities such as in one continuous co-extrusion or a casting or any other type of operation, where each of the layer is formed separately and combined into one layer. In another method, the anodic and the cathodic species (where either one or both type may be electrochromic) are diffused in from the two faces of an electrolyte sheet resulting in anodic and cathodic bands separated by an electrolytic band across the cross-section of this sheet. Yet in another method, an electrolyte sheet may be coated by a spray or a printing process with compositions of anodic materials on one side and cathodic compositions on the other side. In yet another method a solid electrolyte layer is pulled through a liquid bath composition comprising the redox species. The above described diffusible, printable, sprayable or the bath compositions may also have solvents, monomers, and electrolytic components (plasticizers, ionic liquids, salts and polymers) which also deposit on the traveling electrolytic sheet. The dyes may be pre-attached to the polymers in this liquid medium so that they are not able to diffuse deeply in the electrolyte layer and are then dried to remove any solvent that may have been used to impart a desirable viscosity during processing. Alternatively, as the dye laden electrolyte sheet is pulled out, the monomers and/or the dye are polymerized by heat or radiation or react with the electrolytic sheet. Particularly preferred materials for this construction where an electrolyte sheet is pulled through a bath are those solutions that comprise bridged dyes (i.e., a dye having both anodic and cathodic character) so that the same layer may be deposited on both sides. Further, the pre-formed sheets may have more than one anodic and/or cathodic material so that the color or kinetic of the device could be tailored. The preformed sheet may be made so that two releasable layers are placed on either side of it in order to protect this sheet while it is stored or transported. For further protection such sheets may also be placed in bags that are evacuated and then sealed. These release layers and bags may be made out of plastic or metal foils, or plastic coated with metals. Metals and metal coatings will impart superior permeability resistance against oxygen, water and also against light.
The multilayered film to be used for lamination may be cut to size and stored as sheets or rolls that may be later cut to size for lamination. During the processing of these films, an inert atmosphere may be required, particularly when the processing is done at elevated temperature. These layers may be thermoplastic, or thermoset or combination of the two (i.e. partially cured or "b" staged). Before the final EC device assembly, this multilayered structure largely possesses thermoplastic characteristics or has a flowable component so that flowability and good adhesion to the substrates is obtained. During or after the lamination process additional reactions can take place which may cure the film, bind some of the components to the film, etc. These reactions may be triggered by heat or additional radiation processes (such as UV exposure).
For compatibility, all the layers of the composite film may comprise the same or different materials (other than the anodic and cathodic dyes). These materials are polymers, monomers, catalysts, initiators, plasticizers, salts (including ionic liquids), UV stabilizers, viscosity modifiers, etc. These materials may be in the same proportion or in a different proportion for the various layers. The mechanical and ionic properties of these layers may be similar or different. Similar compositions, particularly in terms of the polymers and the plasticizers used promote compatibility and good adhesion between these layers. Once an EC laminate is formed using a pre-formed layer and the substrates, this laminate may be subjected to a radiation (e.g., UV) and/or heat treatment so that further polymerization and/or crosslinking may occur. The extent of polymerization/cross-linking may be different in different layers, or may be none in some of the layers.
Some of the polymers that form the pre-formed layers may be chosen from acrylics (including methacrylics, e.g., polymethylmethacrylate, polyhexylacrylate, polyether acrylates), polyvinylidene fluoride, fluorinated ethylene propylene, polyvinyl acetate, polyvinyl alcohol, polyvinylbutyral, poly vinyl formal, polyurethane, epoxy, silicone, polysulfide, polyethers (e.g., polyethylene oxide and polypropylene oxide) and copolymers comprising these. It is also possible to give a body to these laminates using fillers that result in high thixotropy, e.g., particles smaller than 20 nm such as fumed silica (see U.S. Pat. No. 6,361,709). For ionic materials used in these layers (e.g., cathodic dyes, bifunctional dyes, ionic liquids, salts, or nano-particles with surface attached ionic species) it is preferred that their anions be similar to impart good compatibility. Further, to ensure that these devices are long lasting and have low sensitivity to moisture, the most preferred anions for any of the ionic components are bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N−), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N−) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C−), tris pentafluoroethyl-trifluoro phosphate (PF3(C2H5)3 −). Non fluorine containing anions, for example alkyl sulfate (e.g. C2H5SO4 −) and tetracyanoborate may also be used. To ensure that the solvents have a large electrochemical window and permanency it is preferred that hydrophobic ionic liquids are used as plasticizers. Due to the low vapor pressure of these ionic liquids, these do not migrate or vaporize with time which could lead to change in the device performance or even in the pre-formed film as it is stored prior to assembly. The preferred anions of the ionic liquid are the ones listed above, and the preferred cations include quaternary ammonium, where more preferred quaternary ammonium cations are pyridinium, pyridazinium, pyrrolidinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, tetraalkylammonium, N-methyl morpholinium, cations of the formula [(CH3CH2)3N(R1)]+, wherein R1 is alkyl having 2-10 carbons, cations of the formula [(CH3)2(CH3CHCH3)N(R2)]+, wherein R2 is alkyl having 2-10 carbons, cations having the structural formula
Any of the solvents in the U.S. Pat. Nos. 4,902,108, 6,594,066; 5,140,455; 7,064,212 may be used as non-ionic plasticizers, however the preferred ones are organic carbonates such as propylene carbonate, γ-butyrolactone, sulfolane and phosphates. These plasticizers may be used along with the ionic liquids or without them. Further, the electrolyte layer may only allow transport of non-electrochromic anions and cations such as Li+, Na+, K+, Ca+ and anions such as ClO4 −, BF4 −, CF3SO3 −, N(CF3SO2)2 − (NTF or imide), (CF3CF2SO2)2N−, (CF3SO2)3C−, AsF6 −, PF6 −, Cl−, Br−, tris pentafluoroethyl-trifluoro phosphate (FAP, PF3 (C2H5)3). alkyl sulfate (e.g. C2H5SO4 −) and tetracyanoborate, etc. These ions may also be transported through the anodic and the cathodic layers to provide electrical neutrality. The electrolyte layer in the center of a 3-layer multilayer construction may be a membrane that allows ionic conduction but limits the conduction of the electrochromic anions and cations (e.g., ions of bipyridinium, ferrocene, and phenazine, etc.). This limitation may be due to the large size of such ions. As described later such ions may be bonded to polymeric chains or other particles to increase their size and hence decrease their mobility through the electrolyte layer.
The anodic or the cathodic character to the layer is preferably imparted by putting appropriate EC dyes and/or redox materials in these layers. Each layer may comprise of more than one dye to give the desired color or other characteristics to the device. As an example, the cathodic layer may comprise of bipryidinium salts (viologens) and the anodic layer may comprise of ferrocenes and phenazines. Description of several anodic and cathodic compounds is given in U.S. Pat. Nos. 4,902,108, 6,594,066; 5,140,455; 7,064,212, each of which is included herein by reference. It is preferred that such anodic and cathodic compounds be attached to the polymeric material or nano-particles in these layers so that their mobility across the electrolyte layer is reduced or eliminated, or alternatively, the electrolyte layer in the center should be such that it preferably does not transport electrochromic ions. It is not necessary to add cathodic dye to the cathodic layer and an anodic dye to the anodic layer. One may add bridged dyes to any of these which may have both anodic and cathodic characters. If the bridged dye is added to both the layers, it is only the applied potential polarity in the device which would dictate whether a layer is used as a cathodic layer or as an anodic layer. Many bridged dyes, such as given in the U.S. Pat. Nos. 6,241,916; 6,816,298; 6,961,168; U.S. patent application Ser. No. 11/526,416 are also incorporated by reference herein, some exemplary combinations of bridged dyes with anodic and cathodic characters are viologens bonded to phenazines (or other aryls), viologens bonded to ferrocene, metal-arene complexes, charge transfer compounds, or one or more cathodic moieties bonded to multiple anodic moieties, etc. Electrochromic compounds of the invention also include bifunctional redox dyes having a redox active cathodic moiety that provides the dye with its color properties, and a redox active metal species such as titanium (III), titanium (IV), vanadium (III), vanadium (IV), vanadium (V), iron (II), iron (III), cobalt (II), cobalt (III), copper (I), copper (II), silver (I), silver (II), indium (I), indium (III), tin (II), tin (IV), antimony (III), antimony (V), bismuth (III), bismuth (V), cerium (III), cerium (IV), samarium (II), samarium (III), dysprosium (II), dysprosium (III), ytterbium (II), ytterbium (III), europium (II), europium (III). Bifunctional redox dyes of the present invention that are in the form of metal-arene complexes have the formula
The dyes (cathodic, anodic or cathodic+anodic) may be further attached to molecular energy receptors so that these are stable to UV light (e.g. in US patent application 2002/0012155). These may be molecules or may be nanoparticles of UV absorbing semi-conducting materials such as titania, cerium oxide and zinc oxide. This can impart high UV stability to the system by providing a linked energy receptor. These layers may also have additional nano-particles (including fumed silicas, silsesquioxanes and titania) to provide viscosity and/or UV shielding characteristics. These nanoparticles may also be coated with non-active oxides such as silica, alumina, zirconia and their mixtures (coating is generally about 5-20% of the total thickness or the diameter of the nano-particle). Some of the other preferred nano-particles comprise of silica, silsesquioxanes and tantalum oxide. The particle size of these materials is typically less then 200 nm and preferably less than 100 nm. The attachment of the dyes to the nano-particles is through the functional groups on the surface of such particles. Making of nano-particles and their surface functionalization to be compatible for attachment to polymers or dyes is described in provisional U.S. patent application Ser. No. 60/934,247, filed on Jun. 12, 2007, and U.S. patent application Ser. No. 12/136,407 filed on Jun. 10, 2008 (claiming the priority U.S. provisional 60/934,247), each of which is included herein by reference. One may also use conductive nano-particles such as those comprising indium, tin, zinc and antimony oxides as long as these do not cause an electrical short within the device. For windows one may use dyes that color in the near infra-red so that wider amount of solar energy can be attenuated. Examples of such dyes are described in U.S. Pat. No. 6,193,912.
The anodic and the cathodic materials are not limited to small dye molecules. These may comprise polymeric electrochromic materials or even nano-particles of inorganic materials comprising electrochromic metal oxides and prussian blue. The preferred size of the nano-particles is smaller than 300 nm for clear EC devices, and preferably less than 200 nm, and most preferably less than 100 nm. Examples of electrochromic polymers are polyaniline, polythiophene, polypyrrol and their derivatives. Examples of metal oxides are those comprising tungsten oxide, molybdenum oxide, vanadium oxide, nickel oxide and iridium oxide. The anodic and the cathodic layers may have more than one type of electrochromic materials chosen from the several described above. These polymers or nano-particles are preferably functionalized so that they may be attached to more compatible polymers to make them easily miscible within the anodic and the cathodic layers.
It is preferred that one of the dyes added to the cathodic or the anodic layers be attached to a polymeric chain so as to reduce its transportation across the electrolyte layer. It is also preferred that these dyes be a part of a polymeric network that is crosslinked. As an example, PCT application WO2008/037643 describes a viologen attached to a polymeric material. The attachment may be carried out in several ways, where such dyes are attached to a polymeric chain and then incorporated into the layers (depending on how such layers are produced), or these get attached to the polymer during the extrusion operation, or are attached after the composite layer is fabricated by further subjecting this to heat and/or radiation, or the dyes bond to the materials within the respective layers after the EC devices are fabricated and then subjected to heat and/or radiation. As explained above the dyes may also be attached to the nano-particles where the dye or the nano-particle may be further attached covalently to the polymer in the layer. The dyes may be chemically attached following a variety of chemistries. For example in U.S. Pat. No. 6,420,036 ferrocene with hydroxyl groups is attached in a polyurethane system using isocyanate and polyol monomers with appropriate catalysts. Similarly vinyl ferrocenes may be attached to acrylic and methacrylic matrices using thermal or UV initiated systems. Similarly any anodic or a cathodic dye may be modified by attaching a chemical ligand which may be attachable to the layer. For example, U.S. Pat. No. 4,841,058 describes a viologen dye which is modified to attach an acrylate group so that it can be polymerized into a polymer with similar reactive groups. Each of the patents noted in this paragraph is included herein by reference. Using the same functional groups the dyes may be attached to the nano-particles.
The lamination process of the pre-formed EC layer to the conductive substrates may be carried out using heat and pressure and is described well in U.S. Pat. Nos. 6,995,891 and 6,639,708. These patents also describe the laminate processing, desired strength of the electrolyte layer and adhesion to the substrates in order to acquire characteristics of safety glazing; all such concepts in these patents are incorporated herein by reference. In our invention, the strength of the composite layer and its adhesion characteristics to the substrates has to be similar if it is desired to achieve safety glass characteristics, i.e. adhesion of the electrolyte to give a peel force in excess of 1.8 kg/linear cm width (as measured by 90 degree peel force by American Society of Testing Materials (ASTM) test procedure D3167 or in excess of the electrolyte tensile strength, The thickness of the composite layer should preferably be in the range of 0.2 to 2 mm, and more preferably in the range of 0.4 to 0.9 mm. Exemplary thickness of the electrolyte layer in the multi-layer composite (i.e., without substrates) is about 50% or more of the total thickness of the multilayer. The other layers may be equal or unequal in thickness depending on the coloring efficiency and the redox characteristics. The preferred thickness of the anodic and the cathodic layers is about 50 microns or less. The boundary between the various layers of a multilayer EC film may be distinct or diffused.
The concentration of the dye in the anodic and the cathodic layers in the multilayer film is high, typically higher than 0.05M and preferably higher than 0.1M as all the electrochromic change occurs close to the electrodes, particularly when these materials are not too mobile and are tethered to these layers. The total polymer content in these layers is preferably below 60%. Majority of the balance are plasticizers, salts and/or ionic liquids. To ensure good adhesion between the layers, it is also preferred to have a similar polymer in all of the layer compositions. The anodic and cathodic layers may have additional adhesion promotion or tackifying agents to bond to the substrates. These layers may have lower viscosity or less crosslinking to ensure high tack to the substrates. The concentration of the UV stabilizers, plasticizers, may also be higher for the anodic and the cathodic layers in the multilayer laminatable film.
The EC laminate may be planar or curved depending on the substrates used. Curved assemblies may also be made as taught in U.S. Pat. No. 6,039,390 by incorporating planar EC elements between curved but passive elements. EC Laminate assemblies may also be made in distinct addressable areas for windows and displays as taught in U.S. Pat. No. 6,373,618. The busbars to allow these panels to color uniformly and quickly, especially for large areas is discussed in U.S. Pat. Nos. 6,317,248 and 6,449,082 which are also applicable for use in laminates of this invention. The busbars include internal busbars which are grids or lines of highly conducting materials such as metal wires, meshes and patterns. If these internal busbars are electrochemically reactive, these are passivated on the surface by transparent conductors or other means so that they help in increasing the surface conductivity but do not participate in the electrochemical reactions. Gold lines or busbars may be put on surfaces as it is generally non-reactive in electrochromic devices. Use of these laminates in end-products, such as construction of window assemblies, powering and control of these windows, color choices, etc., are taught in several U.S. Pat. Nos. 6,493,128; 6,528,782 and 6,795,226 which may be applied to the EC laminates of this invention. All of the patents listed above in this paragraph are included herein by reference. As described in these inventions the glass substrates may be chemically or heat strengthened (or tempered). The transparent conductor may be deposited before or after the heat strengthening as long as the transparent conductors do not loose their conductivity, e.g., see U.S. Pat. No. 7,138,181. One may use these laminates in any window construction as discussed in U.S. Pat. Nos. 7,154,657 and 6,369,935.
One may also use polymeric substrates which have conductive coatings. The polymeric substrates may be flexible, preferred thickness for flexible substrates is less than 1 mm, and more preferably lower than 0.3 mm. Some of the substrate examples are polyester (e.g., polyethyleneterephthalate, poly thylenenaphthalate, e.g., Teonex� from Dupont (Wilmington, Del.)), acrylics, polycarbonate. These substrates may also have barrier coatings to stop both oxygen and water migration. These may be inorganic glasses and ceramics such as silica, alumina and titania comprising coatings. Typically the thickness of the inorganic barrier coatings is less than 200 nm. Parylene polymer coatings also result in high barrier properties. Since these are polymeric materials, the coating thickness is several microns. There are several types of Parylene, types C, D and N, and several vendors supply coating services, one such vendor is Para Tech Coating Inc (Aliso Viejo, Calif.). One may also use several layers of inorganic materials and inorganic polymers. One such system is available as Barix™ from Vitex Inc (San Jose, Calif.) which comprises of alternating layers comprising of polymers and inorganic materials (also see US patent application 20070049155). The conductive coatings on the substrates may be transparent conductors such as indium tin oxide (ITO), aluminum doped zinc oxide, fluorine or antimony doped tin oxide and gold. They may also be of the type dielectric/metal/dielectric, where the preferred metals are silver, gold, rhodium, chromium and ruthenium and their alloys, whereas at least one of the dielectric layer is preferably one of the transparent conductive materials listed above. One may also use conductive coatings formed by nano-particles in polymeric species. The nanoparticles are typically rod or wire shaped and may be made of conductive carbon and metals (e.g., silver). Such nano-particle conductive coatings are available from Cambrios Technology Corporation (Mountain View, Calif.). It is important that the conductive layer be in contact with the polymeric layer containing the electrochromic dye or material. One may also take the pre-formed EC film and then deposit conductive nano-particles from solutions (as used by Cambrios, e.g., see published US patent application 20070074316) and then laminate this with conductive or non-conductive substrates to form the final EC device. Flexible EC devices formed using the above substrates after laminating with polymeric EC films may be further laminated between two pieces of glass using standard lamination materials (e.g., Saflex� PVB films from Solutia (St. Louis, Mo.) or Butacite� (Dupont, Wilmington, Del.) between the EC device and each of the glass substrates to provide better protection and impart safety glass characteristics, however in this construction the two conductive sides in the EC device must be accessible for powering the device. It is best to use substrates that are close in refractive index (within 0.05) to the laminating materials described above. Further, in this case the sealant may be applied at the perimeter of the EC device or/and at the perimeter of the glass encapsulation plates. Windows may be made using such EC devices that comprise these conductive films and polymeric electrochromic films, and then further laminated within thicker plastic substrates that may be planar or shaped to give the desired impact resistance and light weight particularly for use in transportation.
A variety of flexible substrates may be used with transparent conductors (e.g., ITO, gold or dielectric/metal/dielectric, or with nano-particles as described elsewhere in this patent). The plastic substrates for any application may be heat stabilized in order to avoid shrinkage or shape changes in the lamination procedure. For example AuARE coatings from CP Films (Canoga Park, Calif.) range from 10-26 ohms/square, with visible transmission of 70% or greater. Such coatings on plastic substrates may be used to make the transportation windows. One may make laminates which have several EC devices stacked in order to get high optical attenuation. In this case a laminating medium (e.g., Safelex� or Butacite�) should be preferably inserted between each EC device. In this invention it is preferred to use substrates for windows which are coated with transparent conductive coatings, wherein the resistivity of such coatings is less than 30 ohms/square and the transmission of the coated substrates is about 70% or greater. Further, since the expansion coefficient of most plastics is larger than most metals and ceramics, and the ceramics have small elongations to break, it is preferred that the total stack of the ceramic transparent conductors (e.g., ITO) when deposited on polymeric substrates be thin, and preferably less than 1,000 nm, and more preferably less than 500 nm. This will keep the stresses in the coatings low and avoid cracking or crazing. The Polymeric substrates may be themselves multilayered or may also have coatings either underneath the transparent conductors or on the opposite surface that provide superior barrier properties, particularly to oxygen and water vapor transport. These may be other polymers (single or multilayers) such as those comprising polyvinylidene chloride, polyacrylonitrile and polyvinylalcohol, or coatings of inorganic materials such as silicon oxide and titanium oxide. The coatings on the substrates may also be configured to result in anti-glare properties, or to impart hydrophobic or hydrophilic properties. The polymeric substrates or the laminatable films may comprise UV absorbers, particularly those are preferred that provide protection in longer UV wavelengths (red shifted), e.g., CGL139 from Ciba Specialty Chemicals (White Plains, N.Y.). Such materials are described in U.S. Pat. No. 6,187,845, which is incorporated herein by reference.
To further increase durability to solar radiation, it may not be enough to only provide the UV blocking mechanisms and materials as is known in the electrochromic literature, but to also lower the transmission in the visible range particularly in the blue and the violets, i.e., preferably blocking between 400 and 420 nm, and more preferably between 400 and 450 nm, and most preferably between 400 and 500 nm before the solar radiation passes through the EC film. Some of the polymers that absorb in lower wavelength visible spectrum are polyimides and polyethersulfones which may be used as one of the substrates. The windows will acquire a permanent color in the bleached state, such as yellow, brown and bronze. Further, when the EC windows are darkened, say to a blue color, i.e. preferably to absorb the longer wavelengths (which is common for most EC materials), the darkening will impart a more neutral color to the window. The conductive coatings may also be optionally used as a resistance electrical heater, for defrosting or provide comfort in the interior.
If only one substrate is blocking the visible light, then it should preferably face the Sun (or outside) for the window application. See
An electrochromic cell was prepared by laminating three free standing flexible polymeric films between two pieces of ITO coated glass. The conductivity of the ITO was 12 Ω/sq.
The first polymeric layer contained the cathodic dye 1,1′dimethyl-4-4′-dipyridium bis(bis(trifluoromethylsulfonyl)imide also known as ethyl viologen 2NTf This dye was prepared by reacting 1,1′dimethyl-4-4′dipyridinium diodide with lithium bis(trifluoromethylsulfonyl)imide in water and isolating the solid product by filtration. The second electrolyte layer acted as an ion conductor and did not contain cathodic or anodic species. The third layer contained the anodic species 5,10-Dihydro-5-10-dimethyl phenazine. The composition to make each polymeric film is given below:
The three formulations above were each prepared in a 100 ml sure seal bottle with a stir bar under a nitrogen atmosphere. Tetrahydrofuran (THE) was used as an easily removal co-solvent to enhance mixing by reducing viscosity. The formulations were heated to 65� C. and stirred until dissolved which took about 3 to 4 hours. All solutions were concentrated by removing THE at 75� C. under reduced pressure and then degassed at 95� C., which resulted in a high viscosity material that could be cast into a film at elevated temperatures. This process took approximately two hours. After degassing the solution was cooled to room temperature and stored under nitrogen prior to using to forming the different layers in the electrochromic cell.
Electrochromic Cell Preparation
An electrochromic cell was prepared using the above layers. The layer placement is schematically shown in
The cell structure above was prepared using the following procedure. Layer #1 material was heated to 95� C. and at the same time, two 4″�4″ aluminum heater blocks were heated to 88� C. A square piece of polyester sheeting was taped onto the bottom aluminum block using polyimide tape. A piece of ITO coated glass was then taped on top of the polyester sheeting. With the ITO coating facing up the hot electrolyte was poured onto the ITO coated glass in the shape of a dog bone. Then a piece of polyester sheeting was placed on top of the electrolyte starting at the center line of the dog bone. A stainless steel draw down rod was used to gently roll the bubbles in the electrolyte from the center to the outside edges. A second top aluminum heating block was placed on top of the polyester sheeting and the complete assembly was left at 88� C. for about 5 minutes. The heating blocks were turned off and the assembly cooled to 60� C. The top block was removed and the coated electrode cooled to room temperature and removed from the bottom block. This composite of glass/ITO/layer #1 was kept covered with the polyester sheeting and was placed in a sealed plastic bag. This same procedure was used to coat a glass/ITO substrate with layer #3.
The layer #2 to be used for combining the two coated substrates was prepared the same way with the exception that it was deposited on the hot block on a polyester film, and once the film was formed and THF removed, it was covered by another polyester film. The two pieces of polyester sheeting acted as release layers. To form the electrochromic device electrolyte #2 film was removed from the polyester sheeting and was carefully placed on top of the glass/ITO/electrolyte #1 stack and on top of this was placed the glass/ITO/electrolyte #3 stack. This gave the following cell configuration:
Glass/ITO/Layer #1 (100 μm)/Layer #2 (300 μm)/Layer #3 (100 μm)/ITO/Glass
Since the polymeric composition of all the three layers is similar, an alternative method is to form all the three films independently with release layers (as the one made for Layer 2) and then place them on the substrate one after the other in the sequence and laminate them all together along with the two substrates. It is desirable to lower the films on each other in vacuum so as not to trap air bubbles, or to draw vacuum on the films prior to lamination under pressure in order to remove entrapped air or gas bubbles.
Yet another high speed method is to co-extrude all the three layers and combine these webs together before these cool down, and then use this film with three layers to laminate the two conductive substrates. The combined film may be stored as rolls, which are cut to size at the lamination plant.
The edges of this device were then sealed with polyimide tape and small binder clips were used to hold the cell together. To color the cell the negative lead was placed on ITO/electrolyte #1 electrode and the positive lead was placed on ITO/electrolyte #3 electrode. The cell was colored at 1.3 volts and shorted to bleach. The data on color kinetics at 550 nm is listed in Table 1.
An electrochromic cell was prepared as described in example 1 except that a bridged electrochromic dye 4-4′bipyridinium1,(4(Ferroceneyl butyl),1 methyl 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide (Fc-Vio Im), was used as the redox species in the cathodic and in the anodic layer the redox species was 5,10-dihydro-5-10-dimethyl phenazine. The formulation for the three different layers is shown below and the cells were prepared as previously described in example 1.
Two cells were prepared and powered at 1.3 and 1.4 volts respectively as shown in Table 2. For cell #1 the initial transmission at 550 nm was 69% T and at a color potential of 1.3 volts it decreased to 20% T in ten minutes. At a power bleach of −1.3 volts the cell went from 17% T to 57% T in ten minutes. The second cell (cell #2) was colored at 1.4 volts and went from 78% T to 31% T in ten minutes. The color potential was applied for another ten minutes and the % T dropped to 24%. This cell was then tested for open circuit stability in the colored state. Under open circuit conditions after 20 minutes the transmission changed from 24 to 40% T. The cell was then shorted and went to 60% T in 20 minutes.
An electrochromic cell was prepared as in example 2 above except that the concentration of the cathodic (bridged dye) and anodic (5,10-dihydro-5-10-dimethyl phenazine) species were increased from 0.02M to 0.04M respectively. Also the thickness of the layers containing the Redox species was reduced from 100 μm to 53 μm. The electrolyte layer thickness was 300 μm. The electrochromic cell configuration was as follows:
Glass/ITO/Layer #1 (53 μm)/Layer #2 (300 μm)/Layer #3 (53 μm)/ITO/Glass
The cell was colored at 1.3 volts and went from 70% T to 8% T in 10 minutes as seen in Table 3. The ΔT for the cell was 62%. The cell was bleached in two ways the first under short circuit and the second power bleached at −1.0 and −1.3 volts as seen in Table 3 and
An electrochromic cell was prepared as in example 3 except that the concentration of the cathodic (bridged dye) and anodic (5,10-dihydro-5-10-dimethyl phenazine) species were increased from 0.04M to 0.08M respectively. Increasing the dye concentration greatly decreased the time to color at 1.3 volts as seen in Table 4. The cell colored from 77% T to 14% T in 28 seconds. The bleach speed also increased and in shorted mode the cell went from 14% T to 72% Tin 71 seconds.
An electrochromic device was prepared as described in example 4 above except that the redox couple was a polymer film of 5,10-Dihydro-5,10-Dimethylphenazine and the other redox component was a spin coated film of poly(3,4-ethylenedioxythiophene) PEDOT doped with polystyrenesulfonate (cationic layer). The different layers comprising the EC device are shown below.
Layers 1 and 2 were prepared as previously described in example 1. The PEDOT layer was deposited from a solution obtained from H. C. Starck (Newton, Mass.) with the trade name Baytron P JET HC. This was spin coated directly onto Layer 2 which was pre-deposited on a glass substrate. The spin speed was 400 RPM to give an equivalent thickness of 120 nm. However, the solution diffused into the top part of the underlying Layer 2. The substrate with the composite coating of PEDOT and Layer 2 was placed in an oven at 55� C. to dry for 5 minutes. This composite coating was then peeled from the glass side and placed onto a clean piece of ITO/glass with the PEDOT side touching the ITO. It was pressed down to achieve good adhesion. Layer 1 was formed on top of a second substrate coated with ITO. The two substrates were assembled together as a laminate with Layer 1 touching the Layer 2. The cell configuration was as follows:
Glass/ITO/Layer #1 (53 μm)/Layer #2 (300 μm)/Layer #3 (150 nm)/ITO/Glass
The edges of this device were sealed with Kapton� tape and small binder clips were used to hold the cell together. To color the cell the positive lead was placed on electrode containing electrolyte #1 and the negative lead was placed on electrode containing electrolyte #3. The results are shown in the Table 5 below.
The same device could have been prepared by an alternative process, where layer 1 and 2 are prepared and combined together as a single composite layer, and then the solution comprising PEDOT is contacted with the layer 2 side of the this composite layer so as to soak the solution to a desired depth into this composite. The composite film could be then used to prepare the final device by laminating between two conductive substrates with the conductive sides touching this composite layer. One may spray the solution of PEDOT on the layer 2 side of the above laminate instead of a soak, or even combine PEDOT within a polymeric material so that it may be formed as film by co-extrusion and combined with the other films before lamination.
A flexible EC device was prepared using thin sheets (˜8 Mil) of polyester (PE) coated with ITO (50 Ω/sq), supplied by CPFilms Canoga Park, Calif., as substrate/electrodes. Between the electrodes the three flexible films were placed containing Redox species (anodic and cathodic species respectively) and electrolyte medium. The three layers were of the following composition and were prepared as described in Example 1.
An EC cell with the structure below was prepared by heating formulation for layer #1 to 95� C.
PE/ITO/Layer #1 (53 μm)/Layer #2 (300 μm)/Layer #3 (53 μm)/ITO/PE
Two 4″�4″ aluminum blocks were heated to 88� C. A square piece of conductive polyester sheeting (coated with ITO) was taped onto the bottom aluminum block using kapton tape. The ITO coating was facing up. The hot electrolyte was then poured onto the ITO coated polyester in the shape of a dog bone. A piece of polyester sheeting was then placed on top of the electrolyte starting at the center line of the dog bone. A stainless steel draw down rod was used to gently roll the bubbles in the electrolyte from the center to the outside edges. The top aluminum heating block was then placed on top of the polyester sheeting and it was left at 88� C. for about 5 minutes. No extra pressure was applied. The heating blocks were then turned off and were cooled to 60� C. The top block was removed and the device cooled to room temperature and then removed from the bottom block. This polyester/ITO/electrolyte layer was kept covered with the polyester sheeting and was placed in a sealed plastic bag. The procedure was repeated to coat a piece of polyester/ITO with formulation for layer #3. Layer #3 was prepared between two pieces of polyester sheeting which acted as release layers and stored in a sealed plastic bag.
The EC device was assembled by sequentially placing first substrate (polyester-ITO)/layer #1, layer #2, layer #3 and second substrate (ITO-Polyester) respectively. This was laminated as described above at 95� C. The edges of this device were then sealed with kapton tape to hold the cell together. To color the cell the negative lead was placed on electrode containing electrolyte #1 and the positive lead was placed on electrode containing electrolyte #3. The EC cell characteristics are shown in Table 6.
Layers 1 to 3 were prepared as previously described in example 6 except that for all compositions glass bead spacers in a size of 300 μm were added. These layers are formed individually between removable films (or rigid glass substrates). Layer 1 and 2 are combined by peeling one of the removable films and combining the two. The two layer composite was then combined with layer three by removing the peelable layers from them resulting in the following
Glass was used for convenience above, but one may have also used flexible film. The glass substrates were removed from both sides resulting in a free standing film comprising all the three layers. This composite film was then used to prepare one device using ITO coated glass as substrates and another using flexible polyester film coated with ITO as substrates. The electrochromic characteristics of the devices are listed in Table 7.
A percent transmission spectrum between 400 and 700 nm of cell#1 using ITO coated glass as substrates is shown in
A polymer electrolyte formulation was made with the following composition, following the procedure in Example 1. Both the substrates for making this EC device were 7 mil heat stabilized polyester film coated with gold (AuARE 14) 14�2 Ω/sq surface resistivity and visible transmission of 74%.
The film was cast on one of the substrates as in Example 1 and then laminated using the other substrate. The edges were sealed in the same fashion. The cell construction was:
The cell performance is shown in Table 8
A free standing film was cast as in Example 1 (layer 2) using the same formulation as above. The visible transmission of the film was 75%. This was then laminated between AuARE14 substrates using the same method as in example 7. The performance is shown in Table 9.
For a window application one could also use AuARE14 substrate on one side, especially the side facing the Sun and the other substrate being ITO coated polymer. A spectrum of AuARE14 substrate is shown in
Another cell was made where the electrolyte was first formulated with the following ingredients.
The electrolyte above was prepared in a 100 ml sure seal bottle with a stir bar. This was done in the glovebox. The sure seal bottle was sealed and then removed from the glovebox. It was heated to 65� C. and was stirred until dissolved. This took about 3 to 4 hours. The solution was then degassed in the fume hood using a vacuum pump. The electrolyte was heated to 75� C. for degassing in order to remove the THF. Once the bubbling was nearly stopped, the temperature was increased to 95� C. and the solution was degassed again. Bubbling decreased after about 30 minutes. The degassing was then stopped and the solution was cooled to room temperature. The sure seal container was then filled with nitrogen gas.
The EC cell above was prepared using the following procedure. The electrolyte was heated to 95� C. At the same time, two 4″�4″ aluminum blocks were heated to 88� C. using thermocouples and a temperature controller. A square piece of polyester sheeting was taped onto the bottom aluminum block using Kapton� tape. The hot electrolyte was then poured onto the polyester in the shape of a dog bone. Another piece of polyester sheeting was then placed on top of the electrolyte starting at the center line of the dog bone. A stainless steel draw down rod was used to gently roll the bubbles in the electrolyte from the center to the outside edges. The top aluminum heating block was then placed on top of the polyester sheeting and it was left at 88� C. for about 5 minutes. No extra pressure was applied. The heating blocks were turned off and were cooled to 60� C. The top block was removed. The film was cooled to room temperature and was removed from the bottom block. The freestanding electrolyte film was removed from between the polyester sheets and was then placed between two pieces of gold coated polyester to make a device.
The edges of this device were taped with Kapton� tape to hold it together. The cell was colored and bleached. Glass spacers were only added to control the thickness of the film. If other casting or extrusion methods are used as are known in making films in the polymer industry, it is not necessary to use the spacers. The electrochromic data for this cell is shown below in Table 10.
The leakage current in the colored state for the device was 0.05 mA/cm2 and the minimum transmission at 1.3V was 14.5%. When the device was shorted to bleach 80% of the range it took 28 s. It was colored again to 11.5% and when left in open circuit mode the same range of bleaching took 592 s.
A glass coated ITO substrate was measured for its transmission from 270 nm to 700 nm at wavelength intervals of 0.5 nm. A polyimide pressure sensitive tape (Polyimide (PI) thickness was 50 μm) was applied to the glass side to block the violet and the blue color transmission and substrate was re-evaluated.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrated and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
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Best Camera at CES: Canon's PowerShot G1 X
Canon's PowerShot G1 X features a 1.5-inch sensor that's almost as large as those found on higher-end (and more expensive) DSLRs. The result is great low-light perfomance and a fantastic picture. Editorial Assistant Alex Wawro tells us all about it.
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Canon PowerShot G1 X Compact Camera
The Canon PowerShot G1 X takes the sharpest photos we've ever seen from a fixed-lens camera, and its image quality and video quality are outstanding overall. However, for $800, we expected better macro...


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Neighbor douses potential house fire
Mattress fire, thought to be put out, catches fire again
CORPUS CHRISTI - A neighbor helped save a home from being destroyed by a fire Thursday morning in the 2400 block of Sarita Street.
Corpus Christi firefighters received the call about 9:15 a.m. from the neighbor, who noticed a smoke odor, Battalion Chief Richie Quintero said.
The neighbor then noticed a mattress on fire in the backyard of the house, got the water hose and put out the majority of the fire before firefighters arrived.
Fire officials believe the mattress originally caught fire inside of the house earlier, because of an electrical cord electrical short. Residents dragged it outside and hosed it down with water.
They thought it was extinguished and left for work, Quintero said.
But the mattress, resting on the side of the house, began smouldering, causing the smoke odor, then reignited. It then caught the house on fire.
No one was home at the time the house caught fire and no one was injured. A kitchen wall was damaged and the water heater was destroyed.
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Home / Promotional Products and Promotional Items / Computer & Office / Paper Clips & Letter Openers / Small Round Paper Clip Dispenser
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- Paper clip dispenser.
- Comes with package of paper clips!
- 24 Hour Ruah and 3 Day Rush service available (see Pricing Information for details).
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- Price includes a one color, one location imprint.
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- 24 Hour Rush and 3 Day Rush service available for quantities up to 1,000 (one color imprint) or 500 (two color imprint).
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Originally written on Fox Sports | Last updated 3/19/13
Quarterback Gunner Kiel is leaving Notre Dame without ever playing a down. Notre Dame coach Brian Kelly announced Tuesday that the former standout from Columbus, Ind., who was one of the top-rated quarterbacks coming out of high school a year ago, plans to transfer. He was the scout team quarterback his freshman season as the Irish went 12-1 and finished the season ranked No. 4. Kelly says Kiel was told he would be given a chance to compete for the starting job. As a senior at Columbus East High School, he passed for 2,517 yards and 28 touchdowns. Kiel originally announced he planned to play for Indiana, then said he would attend LSU before enrolling at Notre Dame.
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25 year old woman | Mooresville, NC, USA | Seeking men 22-38
Beautiful eyes, look for the good in others, beautiful lips, speak words of kindness, & for poise, walk w the knowledge you are never alone.
First let me start out by saying, I am a country girl born and raised. Nothing like a southern belle to bring a smile to a gentlemen's heart. Family and friends are what keeps me focused. I am strong willed and often hard headed but name a southern girl that's not. ;) God walks with me everyday and helps me through all of life's struggles. He is the light in the ever growing dark world. Finding a man just as willing to walk with me in my faith is very important to me. Wanna know more, just ask (:
Coffee and conversation , Cooking , Dining out , Fishing/Hunting , Movies/Videos , Music and concerts , Performing arts , Playing cards , Watching sports , Wine tasting
Aerobics, Dancing, Other types of exercise, Running, Swimming, Weights / Machines, Yoga
I exercise 1-2 times per week.
I have Cats, Dogs, Fish
I would absolutely love to travel outside of the states one day. I've always loved Ireland & if I had to choose a dream vacation it would be there, otherwise locally I'm really fortunate to be halfway to the beach & to the mountains. I love them both
SEC Football is my favorite sport to watch. Although I do watch NFL too. I like to dance & be with family & friends. I might be a rare breed but I really love doing hair as a profession & for fun.
Free time, what's that? Haha I love to just go out, see what's going on, to the movies or to dinner. I like to go fishing & four wheeling & mudding. Getting dirty just makes you appreciate getting dressed up even more. :)
The last thing I actually was able to read all the way through without weeks in between chapters was The Hunger Games series but I read at least a few verses out of my bible daily.
Z{{Cta}} {{#if HasMoreInfo}} ?{{CtaSecondary}} {{/if}}
|What she is looking for
|5'4" (162cms)
|5'9" (175cms) to 6'11" (210cms)
|Body type:
|Slender, About average, Athletic and toned, A few extra pounds
|Blue, Brown, Grey, Green, Hazel
|Light brown
|Auburn / Red, Black, Light brown, Dark brown, Blonde, Dark blonde, Bald
|No Way
|No Way, Occasionally, Daily, Yes, but trying to quit
|Never, Social Drinker, Regularly, Moderately
|Fashion / Model / Beauty
|Administrative / Secretarial, Artistic / Creative / Performance, Executive / Management, Financial / Accounting / Real Estate, Labor / Construction, Legal, Medical / Dental / Veterinary / Fitness, Political / Govt / Civil Service / Military, Retail / Food services, Sales / Marketing, Self-Employed / Entrepreneur, Student, Technical / Science / Computers / Engineering, Law enforcement / Security / Military, Architecture / Interior design
I love my career, I am a hair stylist & there are few things in this world that is better than making someone believe that they are beautiful. Inside & out.
|$25,001 to $35,000
|Less Than $25,000, $25,001 to $35,000, $35,001 to $50,000, $50,001 to $75,000, $75,001 to $100,000, $100,001 to $150,000, $150,001+
|Never Married
|Never Married, Widow / Widower, Divorced
|Have kids:
|Yes, and they live at home (1)
|Yes, and they sometimes live at home, No, Yes, and they live away from home, Yes, and they live at home
|Wants kids:
|Definitely, Someday, Not sure, No, but it's OK if my partner has kids
|White / Caucasian
|White / Caucasian
|Christian / Other
|Christian / Catholic, Christian / LDS, Christian / Protestant, Spiritual but not religious, Other, Christian / Other
I grew up Southern Baptist but I am currently at a non denominational church that I love.
|Associates degree
|High school, Some college, Associates degree, Bachelors degree, Graduate degree, PhD / Post Doctoral


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30 year old woman | Kalamazoo, MI, USA | Seeking men 25-35 within 200 miles
WANTED: Intelligent, Athletic, Fun gentleman to keep up with Ms. Energizer Bunny :)
Hello and thanks for visiting my page ;) Life is a crazy ride so lets grab a hold and explore this big planet together. I'm a young, outgoing, adventurous, intelligent woman who hasn't found Mr. Right yet, but I have been keeping my eyes peeled. I'm looking for a man who enjoys having fun, laughing, is honest, intelligent, enjoys exploring new things... yaaad-yaaad. I am a very busy person who is always on the go. I feel life is too short to miss out on all the great opportunities available. I have a great sense of humor and love to laugh - so I hope you do too. I just finished my graduate degree in Architecture, with a concentration in Sustainability. I am a successful woman who works full-time. You know what they say "those that work hard, play harder" and baby "I hit it out of the park :)" In my free time I enjoy working out; which consists of training for my first full marathon. I enjoy running all types of races - 10Ks, Relays, Half Marathons, the Warrior Dash and excited to do a Tough Mudder. I feel that running is a great way to relieve stress from my hectic lifestyle - it's either that or drink everyday. haha. I thought I would give online dating a try because I prefer not to meet someone in a bar, but so far this hasn't been any better. I also wanted to venture away from the strange men my friends like to set me up with! haha! I value and respect my friends and family - these relationships are some of the most important things in my life. Next, would have to be my career and education. But above all that would be happiness. If you are not happy in life - change it. Your happiness depends on you! I could go on and on, but I'm sure you've already stopped reading by now. haha. Or maybe you didn't even get that far.
Book club , Camping , Coffee and conversation , Cooking , Dining out , Gardening/Landscaping , Hobbies and crafts , Movies/Videos , Museums and art , Music and concerts , Exploring new areas , Nightclubs/Dancing , Performing arts , Playing cards , Playing sports , Religion/Spiritual , Shopping/Antiques , Travel/Sightseeing , Volunteering , Watching sports , Wine tasting
Aerobics, Baseball, Basketball, Dancing, Hockey, Martial arts, Other types of exercise, Running, Skiing, Soccer, Swimming, Tennis / Racquet sports, VolleyBall, Walking / Hiking, Weights / Machines, Yoga
I exercise 5 or more times per week.
I have Cats
Some other viewpoint
I absolutely love to travel. I would quite my job to do so :) Fav places: Central America, Mexico, Hawaii, Europe - France and Switzerland. In the states - D.C., NYC, Chicago, AZ and the Carolina's.
Lawrence Technological University, Southfield, MI
Some of my favorite cuisines include: Thai, Italian, Greek, Spanish, Mexican and Middle Eastern. Some of my favorite things: the beach, dancing, going to movies, wine tasting, reading a good book, shopping, D.I.Y. projects, & going to the Art Hop.
I enjoy watching/ going to the movies, reading, the outdoors - canoeing, kayaking, boating, etc., photography and going to sport events - basketball, hockey and baseball. Oh I love to dance... Doesn't matter what kind of music :)
I enjoying reading a good book (especially on the beach). The last books I read were Water for Elephants, The Girl w/ The Dragon Tattoo, The Help and the Lucky One.
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|5'2" (157cms)
|5'8" (172cms) to 8'11" (271cms)
|Body type:
|Athletic and toned
|Slender, About average, Athletic and toned
|Black, Blue, Brown, Grey, Green, Hazel
|Light brown
|Black, Light brown, Dark brown, Blonde, Dark blonde
|No Way
|No Way, Occasionally, Daily, Cigar aficionado, Yes, but trying to quit
|Social Drinker
|Never, Social Drinker, Regularly, Moderately
|Architecture / Interior design
|No preference
I am truly passionate about my career and future. I want to be successful and have worked really hard to get to where I am. I hope that you have a passion for what you do as well!
|I'll tell you later
|No preference
|Never Married
|Never Married, Widow / Widower, Currently Separated, Divorced
|Have kids:
|Yes, and they sometimes live at home, No, Yes, and they live away from home, Yes, and they live at home
|Wants kids:
|White / Caucasian
|No preference
A lot of Irish.. A little Dutch, English and German!!
|Christian / Catholic
|No preference
I was raised Catholic, but my never baptized. My mother felt this was a grown-up decision and I should be the one to decide.
|Graduate degree
|Bachelors degree
Just graduate w/ a Degree in Sustainable Architecture. Currently have started to study for my 7 licensing exams and be done - at least for awhile!


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Derma E Very Clear® Cleanser -- 6 fl oz
Oops! Something went wrong and we were unable to process your request. Please try again.
Very Clear Cleanser gently removes oil and debris, helps unclog pores, and prevents future breakouts while reducing redness and irritation. This effective cleanser utilizes a special Anti-Blemish Complex of Salicylic Acid, Tea Tree, Willow Bark, Rosewood, Lavender and Chamomile that has been shown to be very effective on blemish-prone skin, Excellent for either oily or dry skin, and will not leave a residue or irritate the skin.
Vitacost price: $16.00
Vitacost price: $7.00
Vitacost price: $8.60


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Hunter Renfroe did not homer in his first Double-A game. He did, instead, in his second.
It happened in the bottom of the eighth. The pitch was a chest-high fastball that was lasered onto the left-field berm at San Antonio's Nelson W. Wolff Municipal Stadium.
Thursday notwithstanding, Renfroe, the Padres' first-round selection in 2013, figures to see fewer of those at this level. In large part, the 22-year-old outfielder earned his recent promotion — following Tuesday's California League-Carolina League All-Star Game — by obliterating Single-A fastballs. With Lake Elsinore this season, Renfroe hit .295 with 16 home runs and 52 RBIs, slugging .565.
In April, he hit .262 with 40 strikeouts. In May, he hit .340 with 28 strikeouts. And in the first half of June, he hit .316 with 13 strikeouts.
"In April, the strikeouts were pretty significant, the average was down," said Randy Smith, the Padres' vice president of player development. "We talked to him about, with his strength, he doesn't have to hit the ball 500 feet. … We kind of pounded that into him, using more of the field, left-center and over.
"The strikeouts went down and the average went up and he maintained the power and the RBIs," Smith continued. "So we thought, 'Let's go to the next level.' He'll see more breaking balls, more breaking pitches when they're behind in the count."
Off-speed offerings loom as an unconquered challenge for Renfroe, though the Padres deemed him more than ready for the Texas League. "He looks like a middle-of-the-lineup hitter," Smith said.
Smith jumps, too
Mallex Smith, another notable Padres prospect to earn a recent promotion, stole his first base for Lake Elsinore on Friday. With low Single-A Fort Wayne, the swift outfielder was already leading all of professional baseball with 48 swipes. Smith, 21, was hitting .295 with a .393 on-base percentage.
Smith spent all of last season with Fort Wayne, hitting .262 while collecting 64 steals.
"His challenge at the next level is becoming a better baserunner," Randy Smith said (Smith was caught stealing 16 times this season with Fort Wayne). "Just better jumps, better routes in the outfield, facing better pitching. We pushed him last year in Fort Wayne. We had him repeat, and he did exactly what we hoped for with an improved on-base percentage and an improved average."
Mallex Smith's progress hit a temporary speed bump Friday. Not long after the steal, he exited with a minor hamstring pull, landing him on the seven-day disabled list.
Fried update
Top left-handed pitching prospect Max Fried is likely two weeks away from beginning his season, Randy Smith estimated. Fried has been dealing with forearm soreness since before spring training. Fried long-tossed from 150 feet on Thursday. "He says he feels great, the doctors say he's perfectly fine," Smith said. "We just need to get him out there and see if he's going to compete."


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30 year old woman | Atlanta, GA, USA | Seeking men 28-38 within 25 miles
Active within 3 days
I want to see the world, AND Fruit roll-ups are AWESOME!
I am from Atlanta, born and raised. However, I left Atlanta to go to college out of state. I love being outside and sitting on a patio for a good Friday happy hour. I find it relaxing to drive around with the Jeep top off listening to music on awesome days ( getting caught singing really loud is definitely embarrassing when there is no cover to hide you face but, I always end up laughing at myself when this happens)! I hope to move to San Diego or somewhere near the water sometime soon( probably wishful thinking). I am completely itching for a change! I'm not a huge fan of the club scene. I am more into the normal everyday bar with live music and beer. I think it's fun getting dressed up every once in a while, but I like wearing flip flops with a cute t-shirt and shorts most days. A lot of my guy friends call me hippie chick...it makes me laugh! Music is a huge passion of mine and I go to a lot of concerts and music festivals. Sports and outdoor activities like paddle boarding are always fun, and I consider myself a pretty athletic person. I do not want a guy who likes to hang out inside playing video games all day. We should be able to have fun staying in cooking and watching a movie or out dancing like idiots. Honestly, dancing like idiots is on the top of my list of favorite things to do. Baseball is my favorite sport! I love the braves and the Cubs...weird I know, but that's what happens when you go to college in the Midwest. Piedmont Park is one of my favorite places to hang out during the spring/ summer. Overall... I am a pretty easy going person who wants to be with someone who challenges me , who shares similar interests and who can bring new and exciting things to the table :). I hope to be with someone who enjoys traveling and the beach. Someone who can make you laugh and be silly with is the best kind to be around! I think you should always be able to have laughter and playfulness in any relationship, romantic or otherwise. A good bear hug always puts a smile on my face and I believe honestly goes a long way. Sorry this section is a bit rough!! I typed it super quick! Do people really read much into these, or do they just look at the pictures? Some of the music I listen to........Avett Brothers, Bon Iver, pretty much anything country, Dave Matthews, Mumford and Sons, David Gray, Elton John, Vampire weekend, My Morning Jacket, Dispatch...you catching the theme..?
Camping , Cooking , Dining out , Fishing/Hunting , Movies/Videos , Music and concerts , Exploring new areas , Performing arts , Playing sports , Travel/Sightseeing , Volunteering , Watching sports , Wine tasting
Baseball, Dancing, Other types of exercise, Running, Skiing, Swimming, Walking / Hiking
I have Dogs
Middle of the Road
The Beach is my favorite place, but I also love the mountains!
Music...I LOVE music.I really enjoy being introduced to new artists that I have never heard of! Favorite shows.........Game of Thrones, Shameless, Californiacation, True blood, Boardwalk Empire, Greys( I am a Female), and Revenge!
Concerts, Festivals, Camping, going to the beach, traveling..anything outside :) playing with my pups! Hanging out at a pool with fun friends, a football to throw and some Ice cold ML.
The Help
Z{{Cta}} {{#if HasMoreInfo}} ?{{CtaSecondary}} {{/if}}
|What she is looking for
|5'8" (172cms)
|5'11" (180cms) to 6'3" (190cms)
|Body type:
|Athletic and toned
|Blue, Brown, Green, Hazel
|Light brown, Dark brown, Dark blonde
|No Way
|No Way
|Social Drinker
|Social Drinker
|I'll tell you later
|No preference
|I'll tell you later
|No preference
|Never Married
|Never Married
|Have kids:
|Wants kids:
|White / Caucasian
|White / Caucasian
|I'll tell you later
|No preference
|Bachelors degree
|Bachelors degree, Graduate degree, PhD / Post Doctoral


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This week, activists across the nation stood togther to demand justice for the people of Sudan. Omar al-Bashir got away with murdering 300,000 people in Darfur. And now he's using the very same tactics in South Kordofan and Blue Nile states where half a million people are at risk of starving to death by the end of this month.
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36352-022: Phase I of the PPPTA: Song Bung 4 Hydropower Project
Project Data Sheet (PDS): Overview
The objective of the PPTA Phase I is to identify the major environmental and social issues associated with the project and review the water usage pattern and the institutional framework for water resource management in the river basin. The PPTA Phase I will also provide the detailed Terms of Reference (TOR) for the preparation of Environmental Impact Assessment (EIA), identify the communities that are likely to be indirectly affected by the Project and propose institutional arrangements for ... Read More
Viet Nam
|Project Number
|Type or Modality of Assistance
Technical Assistance
|Public sector (Sovereign)
|Approval Number
TA No. 4475
|Approval Date
|13 Dec 2004
|Large hydropower generation
|Safeguard Categories
Environment: A
Resettlement: A
Indigenous People: A
Related Projects
Project Data Sheets (PDS) contain summary information on the project or program. Because the PDS is a work in progress, some information may not be included in its initial version but will be added as it becomes available. Information about proposed projects is tentative and indicative.
The Public Communications Policy (PCP) recognizes that transparency and accountability are essential to development effectiveness. It establishes the disclosure requirements for documents and information ADB produces or requires to be produced.
The Accountability Mechanism provides a forum where people adversely affected by ADB-assisted projects can voice and seek solutions to their problems and report alleged noncompliance of ADB's operational policies and procedures.
In preparing any country program or strategy, financing any project, or by making any designation of, or reference to, a particular territory or geographic area in this document, the Asian Development Bank does not intend to make any judgments as to the legal or other status of any territory or area.
View the latest procurement notices for Goods, Works and Related Services, or Consulting Services.


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It's an Internet threat making its way around the country, and now it's hitting in Oklahoma.
The threats come from an Internet flyer calling for the "Oklahoma purge." It's in reference to the 2013 movie by the same name where all crime, including murder, is legal for one night.
According to the flyer, the Oklahoma purge will take place on Aug. 30 from 7 p.m. to 7 a.m. Aug. 31. Law Enforcement officers in the state are aware of the flyer and are monitoring the situation.
Although nothing is expected to come out of this threat, law enforcement officers have indicated that they will be on high alert that night to keep residents of the state safe, stating that it is always better to be safe than sorry.
A similar purge threat had police in Louisville, Kentucky on edge last week. Some people even reported seeing groups of people walking around the city in masks pretending to do the purge, something police said could also cause trouble.
Making light of the situation, residents in other states, where purge threats were made, even threw "purge parties," where guests were encouraged to gather the night of the threat in costume and throw a party. OU students have stated there are plans for parties like this in Norman too.
Police said the best thing residents can do in the actual event of a threat is to report anything suspicious or unusual.