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Mayor and Unions Clash Over Teacher Layoff Plan
Welcome to Politics Bites, where every afternoon at It's A Free Country, we bring you the unmissable quotes from the morning's political conversations on WNYC. Today on the Brian Lehrer Show, Beth Fertig, WNYC's education reporter, discussed Mayor Bloomberg's release of the list of 4,500 teacher positions that would be eliminated if proposed cuts go into effect.
In his plan for teacher layoffs, Mayor Bloomberg has warned that some New York City schools could lose two thirds of their teachers under the "last hired, first fired" layoff rules -- and he's fighting the prospect with hard numbers. His list of 4,500 teacher positions showed what would be eliminated if the cuts go into effect.
The Mayor's plan has been perceived as an attack on unions in a time when the labor is on the forefront of the country's political landscape. (Bloomberg defended himself in an op-ed in the New York Times on Monday, saying he fundamentally supports collective bargaining.) Unions representing teachers and principals in the city call this plan a political stunt to help him end the "last in, first out" policy. But some schools in the city have more inexperienced teachers on staff than others, so if the proposed firings take place under this law, it could affect schools disproportionally.
WNYC's Beth Fertig detailed which schools and teachers could be affected.
The upper east side, for example, is a place that has some new schools and a lot of new young teachers and so that was going to take a hit as well as poor low income areas where there's, number one, high teacher turnover and, number two, a lot of new schools that have opened to replace some failing schools...on the other hand there's places where there's a lot of stability, like Staten Island where teachers tend to go and stay there for a very long period of time and so in Staten Island, only three percent of their teachers would be lost. That's the lowerst percent of any of the districts in the city.
Fertig said another reason you see disproportionate percentages is because the city has to target licensed areas where they think they can manage with fewer teachers.
For example, elementary education. That's a very broad licensed area where you're a classroom teacher. They can do with 2,500 fewer, is the projection, but that's nine percent of all active teachers who are in elementary schools, compared to if you look at music, arts, they're only losing a few hundred teachers, but that's about fifteen percent of all music and art teachers.
There is yet another wrinkle in the number of layoffs based on what teachers are teaching - "new" doesn't always mean the same thing.
They go in different categories of newness, for example. Among the elementary teachers that I mentioned, when the city targeted 2,500 teachers for layoffs because they're the least experienced, they went with teachers who have four years or less. With accounting, which is taught in some of the career classes, they decided they could do with fifty percent fewer of those teachers so they went with anyone with less than fourteen years experience...
Fertig went on to clarify that this plan is not exactly a clear case of firing teachers, either.
If we say that a school would lose 70 percent of its teachers...or 50 percent or 30 percent -- it doesn't necessarily mean they would lose all of those positions. It means that if the principal has the budget and says I want these positions in my school, they could use more senior teachers who are in the 'pool' of teachers that they city pays for, who are without permanent positions... and use teachers who have been let go from other schools -- which is very likely to happen this year with the cuts. [They could say] I'm going to take this more senior elementry school teacher to fill the position by my first year teacher who has to leave, so it doesn't exactly translate into the cuts we think of when we think of teacher losses.
In the planned layoffs, the city has spared special education, ESL and speech pathology teachers.
Some see all of this as a veiled attempt to win something back from the unions — the right to lay off teachers by merit and not by seniority — but Fertig argued the Mayor's been fairly clear about his intentions.
It's definitely a bargaining chip, you can see that politically...He admitted that he wants people to see this. He was asked, are you trying to scare people, and he said, I'm giving them the facts. If you see how this is going to affect the schools, you should call and tell your lawmakers to get rid of last in, first out, or LIFO. So there's defnintely a lot of political pressure building on this.
On Tuesday morning the State Senate's education committee voted to pass the repeal of LIFO, but this is only a start, Fertig said. In the meantime, it seems the unions and the Mayor will continue to battle over this plan.
Whether the firing and the repeal of the law will happen or not, a new system for rating teachers goes into effect next year. Unions argue this is the very reason why there's no need to get rid of LIFO. The Mayor counters that there's a budget crisis in the city, and there's no time to wait.


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Let me start by saying that I am not a racer, maybe someday but not now. I like to ride for fitness and stress relief. I also try to eat decent so I feel better on the bike and life in general. It seems like a few times a year, I pretty much just throw my healthy eating out the window and snack on sweets, eat larger portions, eat things I normally would not, ie fatty foods. I do this and tend to put some weight on, get disgusted and go back to a more balanced diet. Just curious if others do this through the year.
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|Publication number
|Publication type
|Publication date
|28 Mar 1972
|Filing date
|2 Sep 1969
|Priority date
|2 Sep 1969
|Also published as
|Publication number
|Howard G Rogers
|Original Assignee
|Polaroid Corp
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (6), Referenced by (71), Classifications (27)
|External Links: USPTO, USPTO Assignment, Espacenet
OR 3v652t1 9 United 5 Rogers [54] VARIABLE LIGHT-FILTERING DEVICE WITH A REDOX COMPOUND WHICH [451 Mar. 28', 1972 Jonea et al. ..350/l60 Anderaon ..350/ 160 Rogera ..350/160 Manor ..350/l60 Klua at al ..3$0/l60 Primary Exam1nr-Ronald L. Wlbert Arr/nan: Examiner-V. P. McGraw Attorney-Brown and Mikulka Thia invention relate: to
ABSTRACT light flltera employing redox compounda that are aubatantially llght-tranatnittlng in their oxidlzed atate and capable cal upon the addition formed in reaponle to device lightmitting properties, reoxidized, for exa flow.
of forming a atable colored lrec radiol electrons. The colored free radical the flow of electric current rendera the abaorbing.
To mature the original light-tramcolored free radical may be readily mple, by reveraing the direction of current 23 Claim, 11 Drawing Flgurea PATENTEnmza I972 SHEET 1 BF 2 INVENTOR. HOWARD (5. ROGERS fimw n, and m ATTORNEYS PATENTEUMAR28 r972 3,652,149
' SHEET 2 OF 2 F l G. 9
40 40 F I G. ll
HOWARD G ROGERS 6mm amd m ATTORNEYS VARIABLE LIGHT-FILTERING DEVICE WITH A REDOX COMPOUND WHICH FUNCTIONS AS ITS OWN ELECTROLYTE This invention relates to light filters and similar devices employing a redox compound capable of forming a stable colored free radical upon the addition of electrons.
Various systems utilizing an electric current passing through an electrolytic solution to effect a change in the optical density or spectral absorption characteristics of a substance have heretofore been known in the art. One such system involves the alternate plating and unplating of metal at one of the electrodes. Another involves the use of an electrolytic solution of a reversible color-responsive material which changes color or becomes colored upon passing a current through the solution. Basically, these systems have in common a combination of elements, viz., a pair of electrodes separated by a suitable electrolyte, a source of current, and some material or materials which initially may be present in the electrolyte and which, upon impressing a suitable current, exhibit a change in optical density or spectral absorption characteristics, e.g., by plating out or color change from color to colorless or colorless to color.
Such systems generally suffer from at least one of the following shortcomings: too slow; unstable; non-reversible; not automatically or fully reversible; not uniform or consistent throughout the system, particularly over large areas.
It is therefore the primary object of the present invention to provide a novel system for controlling light transmission.
Another object of the present invention is to provide a variable light filter.
Still another object is to provide a variable density window.
Yet another object is to provide non-glare headlamp and windshield systems for vehicles.
Another object is to provide variable density light filter lenses to protect the eyes from brilliant light.
A further object is to provide novel systems for image recordation and image translation.
A still further object is to accomplish the foregoing objectives by providing a reversible system utilizing certain redox compounds whose spectral absorption characteristics are altered instantaneously and automatically upon the addition of electrons in response to the flow of current from a suitable source and restored upon reoxidation.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
The invention accordingly comprises the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others and the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
It has now been discovered that systems capable of a rapid and uniform change in spectral absorption characteristics or optical density to control the transmission of light may be obtained by utilizing certain redox compounds, namely, redox compounds that are substantially light-transmitting in their oxidized state and capable of forming a stable colored free radical upon the addition of electrons whereby they become lightabsorbing. By light-transmitting, it is meant that the compounds are substantially colorless or only faintly colored in their oxidized state so as to transmit substantially all visible light. Upon the addition of an electron, they form an intensely colored stable free radical so as to absorb a substantial portion of light in the visible range.
In contrast to prior electrochemical systems, in the present invention the aforementioned redox compounds may be used in the absence of an electrolyte, i.e., they may be used in the absence of an ionizable material such as an inorganic salt which, upon impressing an electric current, provides ions which will effect the desired change in spectral absorption characteristics. Since an electronic rather than an ionic reduction reaction is involved, the conversion to the free radical occurs very rapidly in response to the flow of current to provide a rapid change in optical density and spectral absorption characteristics. Moreover, the reaction is readily reversible by reoxidizing the free radical which may be accomplished by simply reversing the direction of flow of the electric current and/or by employing an oxidant which may be oxygen or a suitable oxidizing compound.
For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description taken in conjunction with the accompanying drawings wherein:
FIG. 1 is a diagrammatic sectional view illustrating one embodiment of this invention;
FIG. 2 is a similar view illustrating another embodiment of the invention;
FIG. 3 is a similar view illustrating yet another embodiment of the invention;
FIG. 4 is a similar view illustrating still another embodiment of the invention;
FIG. 5 is a cross sectional view of a lens element prepared in accordance with the present invention;
FIG. 6 is a plan view illustrating a variable density window prepared in accordance with the present invention;
FIG. 7 is a parElly schematic vertical sectional view taken i along lines 7-7 ofFIG. 6;
FIG. 8 is a somewhat schematic sectional view showing the use of the present invention in vehicle headlamps;
FIG. 9 is a partly perspective, partly schematic view illustrating the use of this invention to provide glare-free windshields;
FIG. 10 is spatiall diagrarnrhaticIFI- tiEy sectional viewillustrating the use of the present invention in elements for preparing visible images; and
FIG. 11 is a similar view showing the preparation of a visible image with the element of FIG. 10.
In carrying out the present invention, any redox compound may be used including either monomeric or polymeric compounds provided that it is substantially light-transmitting in its oxidized state and capable of forming a stable, colored free radical upon the addition of electrons and provided that it is capable of being alternately and repeatedly reduced to the free radical and reoxidized whereby a reversible change in spectral absorption characteristics or optical density is achieved. As discussed above, the redox compound may be substantially colorless in its oxidized state, or it may be faintly colored so as to be substantially transparent to visible light. Upon the addition of electrons, a stable free radical is formed which is deeply colored and light-absorbing in the visible range.
Examples of redox compounds meeting these criteria are compounds containing a strongly delocalized electron, i.e.,
compounds which have an odd number of 1r electrons distributed over an even number of atoms arranged in a chain. S uch compounds are derived from the general formula X(Y=Y).,X. wherein X is selected from a nitrogen. sulfur and oxygen atom; Y is selected from a nitrogen atom and CH: and n is 0 or a positive integer. A discussion of the chemistry of these compounds is found in International Union of Pure and Applied Chemistry. Vol. l5 (1967) entitled, International Symposium on Free Radicals in Solution." pages l09l22.
Redox compounds of this type which have been found especially useful in the present invention are the so-ealled Weitz radicals as described in the aforementioned reference where X is nitrogen and Y is CH, such as 4,4dipyridylium compounds, diazapyrenium compounds and pyrazidinium compounds. Typically, these compounds are substantially colorless to yellow in their oxidized state and upon the addition of an electron form a deeply colored free radical of intense blue to bluish-purple.
Illustrative of suitable 4,4'-dipyridylium compounds are those having the formula:
R -i-/ ri-R,
wherein R and R each are selected from hydrogen, alkyl, 5
aralkyl and aryl and A is an anion; and polymers thereof having the formula:
wherein A is defined as above and R is either alkylene having 4 to 8 carbon atoms or xylylene and n is at least 2.
Illustrative diazapyrenium compounds are those having the formula:
wherein A, R and R, are defined as above. illustrative pyrazindinium compounds are those having the formula:
. wherein A is defined as above.
Typical of the alkyl, aralkyl and aryl substituents are methyl, ethyl, propyl, isopropyl, butyl, hexyl, benzyl, tolyl, pethylphenyl and phenyl. Typical anions include Br, Cl, 50,, C10,, BF, and tosyl.
Specific compounds encompassed by the above formulas are N ,N-dimethyl-4,4-dipyridylium dichloride; N,N'-diphenyl-4,4'-dipyridylium dichloride; N-ethyl-N'-phenyl-4,4- dipyridylium dibromide; N,N'-dibenzyl-4,4-dipyridylium diiodide;2,2'-dimethyl-N,N'-diethyl-4,4-dipyridylium dichloride; N,N'-dimethyl-2,7-diazapyrenium difluoroborate; N,N'-diphenyl-2,7-diazapyrenium difluoroborate; N,N'- dibenzyl-2,7-diazapyrenium dibromide; 4,5-dimethyl-N,N'- dimethyl-2,7-diazapyrenium dichloride; dipyrido-[ l ,2-a;2',l c]-pyrazidinium dibromide and 3,3'-dimethyldipyrido-[ 1,2- a;2,l -c]-pyra.zidinium dichloride.
Illustrative of the polymeric 4,4-dipyridylium compounds mentioned above are those prepared by reacting 4,4- dipyridyl with an alkylating agent, e.g., 1,8-dibromooctane or 2,2'-dibromo-p-xylene, as described and claimed in copending application Ser. No. 854,781 of Myron Simon, filed on even date herewith.
Upon the application of the appropriate potential, the aforementioned redox compounds are readily converted to a deeply colored free radical, which is sufirciently stable so that the color once formed will remain over a substantial period of time without further application of electric current thereto. In applications where it is desirable to quickly restore the original light-transmitting properties of the compound, the free radical may be readily reoxidized by reversing the direction of current flow and/or by using an oxidizing agent. For example, an electrically stable organic or inorganic electron donor, such as ceric ammonium nitrate or benzoquinone may be admixed with the redox compound. The oxidizing agent also may be atmospheric oxygen and the system suitably 75 vented so that oxygen ions from the air can reoxidize the free radical to restore the original spectral absorption characteristics. Where an aqueous solution of redox compound is employed, the oxygen generated by electrolysis may be used to reoxidize the colored free radical provided that it does not proceed at a rate to cause excessive bubbling. To control electrolysis, other pathways for the current may be provided.
In the present invention the aforementioned redox com-\ pounds may be utilized in either a liquid or solid system. They) may be dissolved in aqueous solution or in an electrically stable organic liquid, e.g., propylene glycol or ethylene glycol monomethyl ether, which additionally may contain viscosity imparting reagents, such as carboxymethyl cellulose. They may be dispersed in a compatible gel, such as gelatin, hydrolyzed polyisopropenyl acetate or hydroxyethyl cellulose, or they may be dispersed in a compatible polymeric matrix, e.g., polyvinyl acetate, polystyrene, cellulose acetate 0 polymethyl methacrylate. It will be understood that the liquid or solid used to dissolve or disperse the compounds will be substantially colorless so as not to interfere with the light transmitting properties of the system. Also, the redox com-\ pounds themselves may be used as their own matrix and the solid redox material simply compressed between the electrodes. In systems where it is desirable to achieve the greatest possible speed in reversibly altering optical density or spectral absorption characteristics, the redox compound is used in high concentrations and preferably is used undiluted, i.e., by itself.
In a preferred embodiment, a solid system is employed which comprises a film of polymeric redox compound made by casting a solution of the redox polymer onto a glass plate electrode. If a polarizing material is desired, the cast film may be stroked in a given direction until oriented.
As indicated previously, the redox compounds of the present invention may be employed without an electrolyte. Sodium chloride, copper perchlorate, acid zinc sulfate, lead nitrate, hydrochloric acid and other ionizable substances commonly used to provide ions to effect color change are not essential to the operation of the systems of the present invention. The redox compounds will function as their own electrolyte and will exhibit a change in optical density or spectral absorption characteristics in response to an electronic reaction. Ifdesired, however, the redox compounds may be used in an ionic system, Le, a conventional electrolytic system employing the aforementioned ionizable substances.
One electrolytic system which has proved especially valuable comprises a saturated solution of a 4,4'-dipyridylium compound in aqueous acid solution. Using about one-tenth to onethird of the total volume of hydrochloric acid with N,N'- dimethyl-4,4-dipyridylium dichloride, an optical density of 3 may be achieved in about microseconds by applying a potential of 500 volts. Besides hydrochloric acid, other organic or inorganic acids may be used as the electrolyte, such as acetic acid, citric acid, sulfuric acid, and nitric acid. Where rapid clearing of the system to its light-transmitting characteristics is desired, an oxidizing agent, e.g., ceric ammonium nitrate may be incorporated into the electrolytic solution. An electrically responsive light-absorbing element utilizing this and other electrochemical systems is described and claimed in application Ser. No. 880,796 by Howard G. Rogers and John J. McCann filed Nov. 28, 1969.
It will be appreciated that the aforementioned compounds will exhibit difierent spectral absorption characteristics at the anode than they will at the cathode. Oxidation reactions will occur and the pH will be acidic at the anode while reduction reactions will occur and the pH will be basic at the cathode. Thus, when the compound is positioned adjacent one of the electrodes, the flow of current is controlled so that this electrode may be either the anode or the cathode and the spectral absorption characteristics of the compound will be determined by the direction of the flow of current.
It will be understood that the above-described redox compounds may be used in conjunction with other oxidationreduction indicators which require the presence of an ionizable material to provide ions for effecting color change. As is well known in the art, all oxidation-reduction indicators change color at a set electrical potential. Thus, the DC. potential necessary to obtain the desired spectral absorption or optical density change will depend upon the potential required for the particular compound employed and will depend in part on the conductivity of the system and cell geometry. It will be apparent to those skilled in the art that the total voltage required for a given compound and a given arrangement of elements may be ascertained by reference to the values for electrical potential given in the literature together with routine experimentation. For greatest efiiciency, the set electrical potential of the above-described redox compounds and conventional oxidation-reduction indicators used should be fairly similar.
The set electrical potential for various oxidation reduction indicators are set forth in the following table wherein the standard value is given when the dye is half oxidized and half reduced.
TABLE P at Color change p Indicator C. Oxidized Reduced Sairauine T 0. 24 Blue-violet Colorless. Neutral red... 0. 24 Red-violet Do. Indigo monosulloni 0.26 D0. Phenosafranine O. 28 Do. Indigo tetrasulfonic acid 0.36 Do. Nile blue N 0.41 D0. Methylene blue 0.53 D0. l-naphthol-Z-sodium sulfonate- 0. 54 Do.
indophenol. Phenol-indo-2, -dlbromolndo- 0. 67 Red Do.
phenol. Blndschedlers green 0.68 Green. Do. Diphenylamine. 0. 76 Violet D0. Diphenylamine-p-sulfon acid 0. 84 Red-violet Do. Erioglaucine A 1.00 Green. Blue-red. Setoglaucine O 1.01 Yellow Yelliwp-Nitrodiphenylamine 1.05 Red-violet. Colorless. Diphenylarnine-2,3-dicarboxylic 1. 12 \iolet Green.
1. 26 Blue Do.
Diphenylarnine-2,2dicarb0Xylic acid.
For a listing of additional oxidation-reduction indicators and acid-base indicators which may be used in conjunction with the redox compounds of the present invention, reference is made to Chemical Indicators, 0. Tomicek, Butterworths Scientific Publication, 195 l.
The use of the above compounds in the practice of this invention will be more readily understood by reference to the drawings.
As shown in FIG. 1, the light filter or light transmission controlling means designated at 1 comprises a pair of spaced, parallel electrodes 2 and 3 which are light-transmitting and a substantially light-transmitting redox compound as described above or a mixture of such compounds 4 confined between and in contact with the electrodes. As discussed previously, where it is desired to rapidly clear the system to restore its original light-transmitting properties subsequent to forming the colored free radical, the direction of current flow may be reversed and/or an oxidizing compound may be used in conjunction with the redox compound. Rather than mixing an oxidizing agent with the redox compound, the device may be vented, in any suitable manner to allow oxygen ions from the atmosphere to reoxide the free radical. Where an aqueous solution of the compound is used, the oxygen resulting from hydrolysis may be employed to clear the system. Depending upon the end use of the filter and the rate at which it is desired to clear the system, current reversal and/or one or more oxidizing agents may be used.
The electrodes 2 and 3 are at least translucent and preferably are substantially transparent to light. They may be any of the light-transmitting electrodes heretofore known in the art, e.g., transparent bases of plastic or glass supporting a thin coating of a conducting metal such as gold, fine mesh screens of a noble metal which may be carried on a transparent support and glass coated with a transparent film of an oxide, such as cadmium, indium or tin oxide. Where the electrodes comprise transparent bases having an electrically conductive surface, they may be used to form opposed end walls of the filter device, provided they are structurally adequate. Alternatively, a separate container may be used to enclose the system.
Electrodes 2 and 3 are connected to a suitable source of electric current by leads 5 and 6, respectively. As shown in FIG. 1, the source of current may comprise a battery 7. Resistor 8 is preferably but not necessarily provided in order to regulate the amount of current. The terminal ends of leads 5 and 6 make contact with double switch 9 to complete the circuit.
In operation, when the switch is in the up" position, as shown in FIG. 1, the. current is caused to flow from the battery through switch 9a to lead 5 whereby electrode 2 becomes the anode and electrode 3 becomes the cathode. Switch 917 of course makes contact with lead 6 to complete the circuit. Thus, electrode 2 pemiits oxidation reactions and electrode 3 permits reduction reactions. That layer of redox compound adjacent the cathode, i.e., electrode 3 is converted to a colored free radical so that a colored filter is obtained.
Where the device is to be cleared by reversing the current flow the direction of current may be controlled manually or it may be controlled automatically, e.g., by means such as illustrated in the bottom portion of FIG. 1. As is shown, this automatic means may comprise a solenoid 11, photoconductive cell 12, battery or other source of current 13 and a resistor 14 connected in series by means of leads l5, 16, 17 and 18, respectively.
As is well known in the art, cell 12 and resistor 14 cooperate to control the amount of current flowing to solenoid 11. When the current is of a predetermined amount, e.g. when photoconductive cell 12 records a relatively low intensity of light, solenoid 11 causes switch 9 to drop to the down position, thereby reversing the direction of the flow of current.
By way of illustration, in a system employing conductive glass electrodes and a dipyridylium compound as the redox material, a change of color from yellow to blue occurs in the vicinity of electrode 3 (cathode) when the switch is in the up" position. Upon reversing the current flow, the original yellowish color is restored to the deeply colored layer adjacent electrode 3, which upon current reversal becomes the anode.
In clearing the device by current reversal it has been found that the best results are achieved by using a slightly lower potential for reoxidizing the colored free radical than the potential needed for the reduction reaction. To reduce a given redox compound to its colored free radical, a certain minimum voltage is required depending upon the set electrical potential of the compound and upon the cell used, i.e., the geometry, the particular electrodes employed, etc. While the colored free radical formed may be reoxidized simply by reversing the direction of current flow and applying the same potential, a colored layer of redox compound tends to form adjacent the opposite electrode which becomes the cathode upon switching the polarity of the system. The formation of color at the opposite electrode may be prevented and the cell visibly cleared by applying a voltage slightly below, e.g., about 0.1 volt below the minimum needed for the reduction reaction. It will be appreciated that the speed with which the compound is reduced to its colored form is in large measure dependent upon the potential applied. Thus, for achieving very rapid color formation, the voltage applied is considerably above the minimum.
In the filtering device described above, only the aforementioned redox compounds are employed. It is also within the scope of the invention to use the aforementioned redox compounds adjacent one of the electrodes and another compound such as a pH or acid-base indicator adjacent the other electrode.
Such a filtering device is illustrated in FIG. 2 wherein a redox compound 4, such as a 4,4'-dipyridylium compound, is
adjacent electrode 3 and another material having reversibly alterable spectral absorption characteristics 40 is adjacent electrode 2. Materials 4 and 40 are separated by a light-transmitting selectively permeable membrane 19, such as cellophane, which prevents migration and admixing of the materials 4 and 40 while permitting the flow of current. The membrane may be eliminated in solid systems where materials 4 and 40 are in a gel or other non-liquid form.
Material 40 may comprise a compound whose spectral absorption characteristics are determined by the pH of the environment, e.g., so-called pI-I or acid-base indicators. Illustrative of such compounds are phenolphthalein which changes from colorless in an acid medium to pink in a basic medium; Malachite Green which changes from green to colorless; Phenacetolin which changes from red to colorless; bromocresol green which changes from yellow to blue; etc.
Another class of compounds useful as material 40 are those which are capable of being alternatively or reversibly reduced and re-oxidized and which exhibit spectral absorption characteristics in the reduced state different from those exhibited in the oxidized state. Examples of such compounds are leuco dyes which typically are colorless in the reduced state and colored in the oxidized state and oxidation-reduction indicators such as Phenosafranine which changes from blue in an oxidizing environment to colorless in a reducing environment; Indigo tetrasulfonate which changes from blue to colorless; diphenylamine which changes from violet to colorless; Erioglaucin A which changes from green to red, etc.
Other compounds useful as material 40 are polymers which exhibit difi'erent spectral absorption characteristics in an acidic versus an alkaline environment Examples of such polymers are S-nitrosalicyaldehyde partial acetal of polyvinyl alcohol which changes from colorless to yellow in basic medium; 3'-formyl-phenolphthalein partial acetal of polyvinyl alcohol which changes from colorless to red in basic medium; etc.
It will be appreciated that material 40 may be dissolved in a solution or dispersed in a gel containing any of the common electrolytes. Also, material 40 may possess or be capable of possessing the same or different spectral absorption characteristics, e.g., the same color or a color different from material Using two separate materials in this manner allows more efficient utilization of a given voltage than is possible with a filtering device as illustrated in FIG. 1. For example, a blue filter, i.e., one which is either blue or substantially transparent, depending on the flow of current may be obtained using a 4,4'-dipyridylium compound, such as N,N-dimethyl-4,4'- dipyridylium (methyl viologen) as material 4 and the oxidation-reduction indicator 2,6-dibromophenyl indophenol as material 40.
Methyl viologen is substantially colorless to faintly yellow in its oxidized state and an intense bluish color when reduced. Conversely, the indophenol is blue in its oxidized state and substantially colorless when reduced. Thus, when current is impressed so that electrode 2 is the anode and electrode 3 is the cathode, both materials 4 and 40 become blue to provide a blue filter, the light transmission characteristics of which are a function of both materials. When the current flow is reversed so that electrode 2 is the cathode and electrode 3 is the anode, the device 1 becomes substantially light-transmitting.
Rather than using the indophenol oxidation-reduction indicator, one may use a pH indicator such as the disodium salt of 5,5'-indigodisulfonic acid, which will be blue in an acidic environment as when electrode 2 is the anode and substantially colorless in a basic environment as when electrode 2 becomes the cathode upon reversal of the current flow. Also, it will be appreciated that where materials 4 and 40 are in a solid form that the membrane 19 is not essential. If desired, material 4 may contain an oxidizing agent.
In the filtering devices previously described, the electrodes are shown to be in parallel relationship with one another. In lieu of this arrangement, the electrodes may be positioned in different relationship with one another and/or may have differ ent shapes. For example, the electrodes may be perpendicular to one another; or one electrode may be coiled around the other electrode. A gross electrode comprising a flat, rectangular light-transmitting electrically conducting plate may be used with a minor electrode comprising a circular or U-shaped rod or wire positioned outside of the useful optical path of the device. In such variations, suitable transparent means may be employed to confine the light-filtering compound.
In the embodiments heretofore described, a pair of electrodes have been employed. However, it is within the scope of this invention to provide variable filters employing more than two electrodes.
In FIG. 3, there is shown a variable flter having three electrodes, two of the electrodes being in parallel relationship with one another, the third being substantially perpendicular to the first two electrodes and outside the field of light-transmittancy of the filter but in contact with the light filtering materials 4 and 40.
As in the embodiment illustrated in FIG. 1, leads 5 and 6 are connected to a suitable source of current. Lead 6a connects electrode 30 to lead 6, so that electrodes 3 and 3a will be of the same potential when current is impressed. Electrode 2, which need not be transparent as it lies beyond the field of light-transmittancy of the filter, is connected by means of lead 5 to the current source.
In one embodiment, materials 4 and 40 are identical in their spectral absorption characteristics so as to provide a variable filter similar in some respects to the filter of FIG. 2. For example, bromothymol blue which is blue in a basic environment and yellowish in an acid environment may be employed as material 40 with methyl viologen as material 4 which is blue in its reduced fon'n and colorless to faintly yellow in its oxidized form. When current is impressed in one direction, both electrodes 3 and 3a are cathodes so that materials 4 and 40 are blue. When the direction of current flow is reversed both electrodes 3 and 3a become anodes, so that both materials 4 and 40 become substantially transparent.
By means of suitable wiring, switches and the like (not shown), either of electrodes 3 and 3a may be disconnected, so that current may be caused to flow to only one of the electrodes 3 and 3a. Thus, it is possible to provide a filter of varying density merely by connecting or disconnecting one of the electrodes. For example, if lead 6a is disconnected, the filtering ability of the system will be a function only of the density of the filter produced at electrode 3. By reconnecting lead 6a, the density is increased due to the light absorption now provided at electrode 3a. Obviously, the connecting and disconnecting may be controlled either manually or automatically.
Where materials 4 and 40 are different, e.g., when they are substantially colorless in one environment and exhibit different spectral absorption characteristics in another environment, three different colored filters may be obtained. Where both electrodes 3 and 3a are connected so that materials 4 and 40 exhibit a color, the resulting filter will be a product of the absorption characteristics of both materials. Alternatively, either electrode may be disconnected to provide a filter of the absorptive characteristics of the color-providing material associated with the respective electrodes 3 and 3a.
It is also contemplated that both the materials 4 and 40 may be the same or different redox compounds of the present invention, e.g., a 4,4-dipyridylium and/or diazapyrenium compound described above. Alternatively, a redox compound, e.g., a 4,4'-dipyridylium compound, may be used as material 4 in this arrangement without another colorchanging material 40. When both materials 4 and 40 are used and are in a gel or other solid form, membrane 19 may be eliminated.
As mentioned previously, in a preferred embodiment of the present invention, the light-filtering redox compound is preferably a polymeric compound, such as, the 4,4'-dipyridylium polymers described above. Polymer films of this type, including molecularly oriented polymer films may be used as materials 4 and 40 in the filtering device of FIG. 3. When oriented films are employed, they may be positioned with their axes of polarization at a predetermined desired angle, for example, at right angles for potential total extinction of light. When current is impressed so that electrodes 3 and 3a are cathodes, a pair of deeply colored blue light polarizers are formed having their axes, for example, at right angles thereby permitting a minimal amount of light to be transmitted through the filtering device. When the current fiows in the opposite direction, the oriented films lose their polarizing properties with respect to visible light, and the films change from blue to their original yellowish color. By employing suitable wiring the variable filter of FIG. 3 is capable of providing a pair of polarizers or a single polarizer at either of the electrodes 3 or 3a.
Another embodiment comprising a polarizing system is illustrated in FIG. 4 wherein a permanent polarizer 40 is provided on the side of electrode 2 opposite an oriented dipyridylium polymer film 4. Polarizer 40 also may be placed on the other side of the electrode 2 provided that it will allow the passage of current and is electrically stable. The permanent light-polarizing sheet 40 may also be positioned on the outer surface of electrode 3. As in the above embodiment, the layer of polymeric material 4 adjacent electrode 3 forms a blue light polarizing film upon the addition of electrons and upon reoxidation reverts to its original yellowish color. Reoxidation may be achieved by using an oxidizing agent and/or by reversing the direction of current flow.
In view of the foregoing illustrative embodiments, other variations in the structure and/or the arrangement of elements of the novel filtering device of this invention will be readily suggested to those skilled in the art.
The light-filtering devices of this invention are capable of a variety of different uses in which a stable, unifonn instantaneously variable light filter is desirable or necessary. They may be employed, for example, in lens elements for goggles or shields for protecting the eyes from bright light. A typical lens element is shown in FIG. 5.
As shown therein, the element comprises a transparent lens having opposed faces and the novel filtering device 1 as shown, for example, in FIG. 1 in juxtaposition with and coextensive with one faceof the lens. The filter l is connected by leads (not shown) to a suitable source of current. The filter 1 may be bonded to the lens 10 using any suitable lighttransmitting adhesive, e.g., an epoxy resin.
It will be appreciated that a single such lens element may be used as an overall shield or two such elements may be used to protect the eyes and the element(s) mounted and cemented in a suitable frame provided with openings to accommodate the leads for connecting the filter element to a source of current.
The novel filters of the present invention also find utility in variable density windows for controlling the amount of light entering a room or other enclosure. A typical variable density window is illustrated in FIGS. 6 and 7.
As shown therein, the variable density window comprises a recessed or grooved frame or mount of a suitable non-conductive material such as wood confining the novel filtering device 1 as shown, for example, in FIG. 2 between a pair of transparent non-conducting plates 21. The filter l is connected to a suitable source of current by leads (not shown) passing through frame 20.
Where found expedient or desirable to do so, filter l and plates 21 may be laminated together at the top and bottom by means of a suitable bonding material to provide a unitary structure. Suitable bonding materials such as epoxy resins, vinyl acetate resins, etc. will be readily suggested to those skilled in the art. It is also contemplated that a polarizing filtering device may be used, such as shown in FIG. 3, wherein materials 4 and 40 comprise a molecularly oriented 4,4- dipyridylium polymer film. Also, a pair of polarizing or nonpolarizing filtering devices, each with its own protective plate or plates, may be provided on either side of frame 20 in which event the two devices may have an air space therebetween.
In controlling the amount of light entering a room or other enclosure, a maximum amount of current may be generated to provide a variable filter with maximum light absorption characteristics in response to maximum brightness. Conversely, in minimal brightness the flow of current may be automatically reversed to render the filtering device instantaneously light transmittant. Rather than reversing the current, reoxidizing to clear the system may be accomplished by chemical means using an oxidizing agent. For example, the system may be suitably ventilated to allow the redox material to be reoxidized in air.
The present invention is also useful in systems for providing non-glare and fog-penetrating headlamps for vehicles. It is contemplated that the present invention may be employed in automobiles and the like where the headlamps may be instantaneously rendered non-dazzling and/0r fog-penetrating by applying an electric current in a given direction. When the direction of flow of current is reversed, the headlamp permits light to pass in muchthe usual way. The vehicle battery may be employed as the source of current and the direction of current flow may be controlled either manually by the occupant or automatically by a photoelectric cell or the like adapted in the manner illustrated in FIG. 1, to reverse the flow of current when motivated by the light from an oncoming vehicle.
FIG. 8 illustrates somewhat schematically a headlamp of this invention. As shown therein, a typical headlamp 22 has a light bulb 23, a reflector 24 and a transparent protective cover 25 of glass or the like. The variable light filter 1, such as shown 7 in FIG. 1, is positioned at some point between bulb 23 and cover 25 and mounted in a frame 26 or the like. Frame 26 is provided with a suitable opening through which leads 5 and 6 are connected to a suitable external source of current, e. g., the
vehicle battery, although the headlamp assembly may be provided with its own source of current if desired. Also, it will be appreciated that the device 1 need not be behind the cover 25 nor that cover 25 is essential but that the arrangement shown affords protection for the assembly.
In use, the headlamp is normally substantially similar to conventional headlamps in terms of the transmittance of light emitted from bulb 23. In other words, with a variable filter such as illustrated in FIG. 1, the redox material 4 is substantially transparent until the current is caused to flow through lead 5 to electrode 2 so that electrode 3 becomes the cathode and material 4 becomes colored to render the light transmitted non-dazzling. When oriented polymer films are employed, the material 4 is light-polarizing upon changing color. Upon reversal of the flow of current, material 4 once more becomes substantially light-transmitting and non-polarizing to visible light so that light emitted from bulb 23 is again transmitted in much the conventional manner.
The present invention is also particularly useful in polarizing systems for providing glare-free windshields. Systems employing polarizing Windshields to protect the occupants of a vehicle from the glare of oncoming headlights are well known in the art and, are disclosed, for example, in U. S. Pat. Nos. 2,031,045; 2,087,795; and 2,440,133.
Essentially such systems employ a polarizer in the windshield and a polarizer in the headlamps, each having the same axis of polarization forming approximately a 45 angle with the vertical.
With two vehicles equipped in this manner approaching from opposite directions, the headlamp polarizer of one vehicle would have its axis of polarization perpendicular to that of the windshield polarizer of the second vehicle.
In this case, the light from ones own headlamps would be visible through the windshield, while the glare from oncoming headlights would be eliminated. However, a windshield provided with a polarizer in the manner heretofore known in the art has the inherent disadvantage of tending to obscure vision in certain instances by decreasing the intensity of transmitted radiation at times when the maximum intensity of transmitted radiation is desirable.
The present invention obviates this inherent disadvantage by providing a system whereby a normally transparent windshield may be rendered light-polarizing only at desired intervals, e.g., when it is desirable to prevent glare from oncoming headlights.
FIG. 9 illustrates the use of this invention in anti-glare systems for vehicles.
A vehicle 30 has its windshield 31 provided with a filter device such as illustrated in FIG. 1 having a molecularly oriented film of a redox compound, e.g., a 4,4'-dipyridylium polymer, capable of exhibiting light polarizing properties when current is impressed in a given direction actuated automatically by the intensity of light emanating from the headlights of an oncoming vehicle. The headlamps 22 also are provided with polarizing units which may be the conventional polarizers heretofore suggested for such usage. The polarizing units also may comprise the reversible polarizing systems of the present invention. The axes of polarization of the respective polarizers are the same and are approximately at a 45 angle to the vertical as shown by the diagonal lines.
The windshield 31a of a second vehicle equipped in similar manner would have a variable filter having an axis of polarization (viewed from within) as shown by the diagonal lines. In other words, the axis of polarization of the windshield of one vehicle will have an axis of polarization perpendicular to that of the headlamps (and windshield) of a second vehicle ap-' proaching from the opposite direction.
In the manner heretofore described, the light emanating from the approaching headlamps and striking the photoconductive cell of the filtering device would automatically and instantaneously cause the redox material in the light filter in the windshield element to become deeply colored and light polarizing and thus, eliminate glare from the oncoming vehicle. When the vehicle has passed, the process is automatically and instantaneously reversed whereby the redox material returns to its original light-transmitting condition.
It is also contemplated that the variable filter device associated with the windshield may also contain at least a second layer of redox material capable of providing a polarizer with its axis of polarization vertical, so as also to reduce glare from sunlight reflected off the road surface. In such a system, the variable filters of FIGS. 2-4 are particularly useful. It will be understood that the non-polarizing systems of the present invention also may be used to provide non-glare auto vehicle systems.
The present invention is also useful in photographic processes for image formation or translation, particularly in the field of document duplication.
FIGS. and I1 illustrate this aspect of the present invention. As shown in FIG. 10, a photographic unit of this invention may comprise, in order, a first transparent electrode 2, a photoconductive layer 27, a redox material 4, such as the 4,4- dipyridylium compounds described above, and a second electrode 3.
Photoconductive layer 27 comprises a layer of a photoconductive material, e.g., a material which is rendered electrically conductive in its transverse direction only upon exposure to light. Materials having this characteristic and their preparation are well known in the art and per se comprise no part of the present invention. Examples of such materials include cadmium sulfide, selenium, etc.
In FIG. 11 which illustrates the use of the photographic unit of FIG. 10, a document or other object 29 to be reproduced having transparent areas 29a is placed between a suitable source of light 28 and the photographic unit. Light passing through areas 29a render corresponding areas 270 of photoconductive layer 27 electrically conductive. This imagewise conductivity is employed to provide a visible image in the following manner.
When electric current is impressed, an imagewise change in the spectral absorption characteristics occurs in areas 4a of redox material 4. Material 4 is initially light-transmitting so that areas 4a become colored upon impressing the current to provide negative image. Subsequent to image formation, the current either may be left on or switched ofi" and the resulting image viewed by reflection through transparent electrode 3.
Where material 4 is a molecularly oriented redox polymer as described above, a polarizing image is obtained. When the polarizing image prepared in this manner is of such low con- 5 trast as to be faint, it may be viewed through a polarizer or analyzer, the polarizing axis of which is crossed with that of the polarizing surface on which the image is formed. In a known manner stereoscopic images also may be formed by superimposing a pair of polarizing images with the polarizing axis of one at right angles with the polarizing axis of the other. Where the polarizing images are of high contrast, they are particularly useful in advertising displays and the like which rely for appeal on unusual optical effects.
Various changes may be made in the structure of the photographic unit of FIG. 10 without departing from the scope of the invention. For example, it is contemplated that a metal layer could be placed on the back of the photoconductive layer to facilitate viewing of the image by reflection. Also, a light-absorbing element could be placed between the layer of redox material 4, and the photoconductivelayer 27 to prevent unwanted changes in conductivity of layer 27 resulting from viewing light entering the back of the photographic unit through electrode 3.
The images prepared in the foregoing manner may be erased by subjecting photoconductive layer 27 to an overall exposure and continuing the fiow of current in the same direction. The overall exposure will render photoconductive layer 27 uniformly conductive which in turn causes a uniform change in spectral absorption characteristics of redox material 4. The colored material may be reoxidized to its colorless form by exposure to atmospheric oxygen or by using an oxidizing compound in admixture with the redox material. Alternatively, the original light-transmitting properties of the redox compound may be restored by simply reversing the direction of current flow.
Once the image has been erased," a new image may be fonned and the unit used repeatedly. Also, the images produced may be permanently recorded using conventional or difi'usion transfer photographic techniques before they are erased.
In the foregoing description of the many uses of the novel filters of this invention, a single such filter has been employed.
It is contemplated that a plurality of such filters may be employed, if desired. For example, two or more filters may be connected in series to provide increased filtering capabilities.
The following examples are given to further illustrate the present invention and are not intended to limit the scope thereof.
EXAMPLE 1 A light-filtering cell was constructed by cementing along three edges a pair of spaced, parallel rectangular conductive glass electrodes. The light-transmitting conducting tin oxide coatings of the electrodes were positioned so as to face each other, and the electrodes were connected to a source of DC current. The space between the electrodes was filled with a saturated solution of N,N'-dimethyl-2,7-diazapyrenium difiuoroborate in water. The solution was light orange in color and after applying a potential of 3 volts DC across the cell, the layer of solution in the vicinity of the cathode turned green. The application of current was discontinued and the solution allowed to clear to its original orange color upon exposure to atmospheric oxygen.
EXAMPLE 2 Using the apparatus of Example 1, the cell was filled with a saturated solution of dipyrido[ l,2-a;2',l',-c]-pyrazidinium dibromide in water. The solution was pale in color and upon applying a potential of 3 volts DC across the cell, the solution in the vicinity of the cathode turned yellow-brown. After discontinuing current flow, the solution cleared to its original pale color upon exposure to atmospheric oxygen.
EXAMPLE 3 Example 1 was repeated using a saturated solution of N,N- dimethyl-4,4-dipyridylium dichloride which was faintly yel- EXAMPLE 4 Example 3 was repeated using N,N'-dimethyl-4,4'- dipyridylium dichloride except that a potential in excess of 2.3 volts DC was applied in one direction across the cell whereupon the layer of solution adjacent the cathode turned from yellow to a deep blue-purple, and then the direction of current flow was reversed and a lower potential of 2.1 volts applied whereupon the solution cleared to its original yellow color.
EXAMPLE 5 Example 1 was repeated except that a saturated solution of N,N'-dibenzyl-4,4'-dipyridylium dichloride in water was employed. The solution turned a deep blue in the vicinity of the cathode when a potential of 3 volts DC was applied across the cell. The flow of current was discontinued and the solution allowed to stand in air whereupon it cleared to its original yellow color.
EXAMPLE 6 Example 1 was repeated except that a saturated solution of N,N'-dimethyl-4,4'-dipyridylium dichloride in ethylene glycol monomethyl ether was employed in the cell. The solution changed from yellow to deep bluish-purple adjacent the cathode when a potential of 2.5 volts DC was applied. The solution cleared to its original yellow color upon standing in air after current flow was discontinued.
EXAMPLE 7 Example 1 was repeated except that the cell was filled with a saturated solution of N,N-dimethyl-4,4'-dipyridylium dichloride in aqueous hydrochloric acid electrolyte which contained 0.2 cc. of a saturated aqueous solution of ceric ammonium nitrate per 16 cc. of electrolyte. The electrolyte contained 50 percent by volume acid.
Upon applying a potential of 2.3 volts DC across the cell, the solution adjacent the cathode turned an intense blue-purple. Substantially simultaneously with discontinuing current flow, the solution cleared to its original yellow color.
EXAMPLE 8 A layer of dry poly-N,n-butylene-4,4"dipyridylium dibromide was compressed between a pair of transparent conductive glass electrodes having their conductive tin oxide coatings facing inwardly and contiguous with the opposed surfaces of the polymer layer. The electrodes were connected to a source of DC current and a potential in excess of 1.5 volts was applied across the cell. Upon applying the current, the layer of polymer adjacent the cathode changed from pale yellow to an intense bluish-purple. After the flow of current was discontinued, the polymeric layer cleared to its original yellow color upon exposure to atmospheric oxygen.
The poly-N,n-butylene-4,4-dipyridylium dibromide,
used in the above assembly was prepared as follows. A solution of 3.9 gm. 4,4dipyridyl and 5.4 gm. of 1,4-dibromobutane in 175 of dry Z-methoxy ethanol was refluxed and stirred under nitrogen for 5 hours. The precipitated product was filtered off while hot, washed with Z-methoxy ethanol and then acetone. The product was dried in vacuo. Product yield was 2.5 gm.
EXAMPLE 9 The polymer prepared in Example 8 was spread on the conductive tin oxide surface of a conductive glass plate electrode and stroked in one direction with polished wood until it was clear. A second transparent conductive glass electrode was positioned on the film with its conductive surface contiguous EXAMPLE 10 The polymer prepared in Example 8 was admixed with gelatin to give a blend containing about percent by weight polymer and 20 percent by weight gelatin. The resulting mixture was spread in a thin film on the conductive tin oxide surface of a conductive glass plate electrode, and as the second electrode, a light-transmitting layer of gold was evaporated on the free surface of the polymer blend. The electrodes were connected to a source of D. C. current, and a potential in excess of 1.5 volts was applied across the cell whereupon the film changed color from yellow to blue in the vicinity of the cathode. After current flow was discontinued, the film cleared upon standing in air to its original color.
Since certain changes may be made in the above apparatus, product and process without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
1. A light-filtering device comprising a layer of a light-transmitting redox compound (a) capable of functioning as its own electrolyte and (b) capable of forming a stable colored free radical upon the addition of electrons and means for flowing an electric current in a predetermined direction through said layer, said redox compound being the sole electrolyte.
2. A variable light-filtering device comprising a pair of spaced, parallel, coextensive light-transmitting electrodes, a layer of a light-transmitting redox compound (a) capable of functioning as its own electrolyte and (b) capable of forming a stable colored free radical upon the addition of electrons confined between said electrodes and means for flowing an electric current in a predetermined direction through said device, said redox compound being the sole electrolyte.
3. A device according to claim 2 wherein said layer contains an oxidizing agent.
4. A device according to claim 2 including means for reversing the direction of current flow.
5. A device according to claim 4 including means for automatically predetermining said direction of current flow.
6. A device according to claim 2 wherein said layer comprises a solution of said redox compound in a light-transmitting solvent.
7. A device according to claim 6 wherein said solvent is water.
8. A device according to claim 6 wherein said solvent is an electrically stable organic liquid.
9. A device according to claim 2 wherein said layer comprises said redox compound in a light-transmitting solid matrix.
10. A device according to claim 9 wherein said matrix is a gel.
11. A device according to claim 9 wherein said matrix is a polymer.
12. A device according to claim 2 wherein said redox compound is a polymer.
13. A device according to claim 2 including a third electrode in contact with said layer of compound and positioned outside the field of light-transmittancy of said pair of lighttransmitting electrodes, and means for maintaining said pair of light-transmitting electrodes at the same potential and said third electrode at a different potential.
14. A device according to claim 2 wherein said compound is a diazapyrenium compound.
15. A device according to claim 14 wherein said compound is N,N'-dimethyl-2,7-diazapyrenium difluoroborate.
16. A device according to claim 2 wherein said compound is a pyrazidinium compound.
17. A device according to claim 16 wherein said compound is dipyrido[ l,2-a;2,1'-c]-pyrazidinium dibromide.
18. A device according to claim 2 wherein said compound is a 4,4'-dipyridylium compound.
19. A device according to claim 18 wherein said compound is N,N-dimethyl-4,4-dipyridylium dichloride.
20. A device according to claim 18 wherein said compound is N,N'-dibenzyi-4,4-dipyridylium dichloride.
21. A device according to claim 18 wherein said compound is poly-N,n-octylene-4,4'-dipyridylium dibromide.
22. A device according to claim 18 wherein said compound is poly-N,n-butylene-4,4-dipyridylium dibromide.
23. In an enclosure provided with transparent means for transmitting light from an external source into said enclosure, the improvement which comprises positioning in coextensive relationship with said transparent means, a light-filtering device as defined in claim 2.
l i t k
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|Gentex Corporation
|Electrochromic device having an improved fill port plug
|16 Oct 2009
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|Donnelly Corporation
|Rearview mirror assembly for vehicle
|9 May 2008
|5 Jun 2012
|Donnelly Corporation
|Vehicular video mirror system
|8 Feb 2011
|1 Jan 2013
|Gentex Corporation
|Electrochromic device having an improved fill port plug
|31 Dec 2012
|18 Nov 2014
|Gentex Corporation
|Electrochromic device having an improved fill port plug
|12 Mar 2014
|16 Jun 2015
|Gentex Corporation
|Fill port plugs for electrochromic devices
|20 Aug 2014
|8 Sep 2015
|Gentex Corporation
|Electrochromic device having an improved fill port plug
|1 Oct 2004
|14 Apr 2005
|Donnelly Corporation
|Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices
|18 May 2005
|5 Jan 2006
|Genzyme Corporation
|Ionene oligomers and polymers
|15 Jun 2006
|1 Feb 2007
|Fitzpatrick Richard J
|Ionene polymers and their use as antimicrobial agents
|24 Mar 1987
|7 Oct 1987
|Gentex Corporation
|Single-compartment, self-erasing, solution-phase electrochromic devices, solutions for use therein, and uses thereof
|29 Apr 1987
|4 Nov 1987
|Cis Bio International
|Process for the photochemical cleavage of nucleic acids by 2,7-diazapyrenium dications, and diazapyrene derivatives
|7 Aug 1991
|12 Feb 1992
|Max-Planck-Gesellschaft zur F�rderung der Wissenschaften e.V.
|Electrochromic device
|29 Apr 1987
|5 Nov 1987
|Oris Sa
|Method for the photocleavage of nucleic acids by using 2,7-diazapyrenium dications, new diazapyrenic derivatives
|20 Sep 1999
|30 Mar 2000
|Gentex Corp
|Improved seal for electrochromic devices
|16 Mar 2000
|5 Oct 2000
|Bayer Ag
|Flat electrochromic contrast system
|30 Sep 2003
|15 Apr 2004
|Gentex Corp
|Environmentally improved rearview mirror assembly
|U.S. Classification
|359/275, 546/257, 546/66, 546/258, 359/266, 544/252
|International Classification
|Cooperative Classification
|European Classification


text:
Best ~ Antique 1800s ~ Decorator Folk Art Wood Rawhide Book Stand ~ Saddle Tree For Salei000000
~ BEST! ~ ANTIQUE 1800's ~ DECORATOR FOLK ART ~ WOOD & RAWHIDE ~ BOOK STAND ~ SADDLE TREEClick to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge Click to Enlarge
Fine Antique 19th C. Folk Art rawhide laced wooden saddle tree / book shelf from South of the Border, down Mexico way. This is the best one I have owned, and the best one I have seen of this type that is not silver embellished. It appears to be in unused condition, and never fitted with leather for a saddle. It is very interestingly constructed by using wooden pegs and rawhide lacing's to hold it together. This suggests that it is an early piece, and dates to the late 19th century; not only because of the construction method, but also due to the dark aged patina overall. This piece is in 100% original and complete untouched patina that collectors love to see. Note that at the base of the horn where it meets the frame, there is only one wedge fitted in this 90 degree angle. The one side has a wedge with a wooden peg affixing it to the frame. The other side does not have this wedge, nor is there an indication that there was ever a hole for the wooden peg. Thus, it was made this way; perhaps uncompleted, perhaps intended that way. In any case, it is completely original. There are 2 iron nails that along with the rawhide lacing, help hold the top of the saddle back on, that appear to be hand made. Perfect as a book rack, Western, Western Americana, Cowboy, Vaquero, Old West, Horseman, Horse Trapping, Equestrian, saddle, saddle tree display; or as a decorating / Folk Art conversation piece; or use as a book stand, placing the corner of the books in the middle channel. Weight is estimated at 7 lbs.
FREE U.S.A. SHIPPING, HANDLING & DELIVERY or SIGNATURE CONFIRMATION
FOR USA PURCHASES, SHIPPING, HANDLING & DELIVERY or SIGNATURE CONFIRMATION IS FREE VIA U.S.P.S. FIRST CLASS MAIL (UP TO 14 OZ.) OR U.S.P.S. PRIORITY MAIL USING ONLINE SHIPPING LABELS WITH EMAIL CONFIRMATION. REQUIRES A SIGNATURE CONFIRMATION FOR ALL ITEMS $250 OR MORE. PLEASE MAKE DELIVERY ARRANGEMENTS FOR ITEMS REQUIRING A SIGNATURE AS PROOF OF RECEIPT. does not allow optional or required buyer selected shipping insurance. Sellers cannot charge the buyer a separate fee for insurance in a listing or after the buyer has committed to purchase the item, and cannot indicate insurance is only offered upon buyers request. For items $1,000 and over, buyer has the option to pay additional costs for U.S.P.S. Express mail with tracking. All items are shipped within 1 to 2 business days with email confirmation. Items shipped to a California address require CA State sales tax of 8.625% or a valid CA seller's permit #, or the item can not be shipped. Items shipped to a U.S.A. address and paid for using PayPal and shipped via PayPal or online shipping service are covered for non-delivery by their shipping service with delivery confirmation or signature confirmation. PayPal requires the buyer to have a Verified U.S.A. Account, make a single payment from one account & ship the item to the U.S.A. address on the transaction details page.
PAYPAL & ELECTRONIC FUNDS TRANSFER, e-CHECKS & ALL MAJOR CREDIT & DEBIT CARDS THROUGH PAY PAL. PREPAID NEGOTIABLE U.S.A. PAPER BANK DOCUMENTS & PERSONAL BANK DRAFTS DRAWN ON A U.S.A. BANK CONSIDERED WITH PRIOR APPROVAL.
BUYER MUST CONFIRM HIGH buyer STATUS WITHIN 48 HOURS after the end of the sale; and PAYMENT MUST BE RECEIVED BY ME WITHIN 3 CALENDAR DAYS (electronic payment) OR 5 DAYS (paper payment with pre-approval) of the sale's end; otherwise, seller reserves the right to cancel the sale and report you to as a non-paying buyer. Seller reserves the right to relist an item if 's system goes down within 12 hours of the end of the sale. offers will not be accepted from anyone that is not a registered user. Seller reserves the right to cancel offers from any er who has an unsatisfactory transaction history, has changed their user Identity in the previous 30 days, or whose rating is listed as private.
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text:
Journal of Acute Disease
Journal of Acute Disease (JAD) is a quarterly international medical journal dedicated to promoting and disseminating original, peer-reviewed work in the field of acute diseases and related medical specialties by publishing high quality scientific and clinical research worldwide. The articles published mainly deal with pre-hospital and hospital emergency medicine, Intensive Care Unit, critical care, disaster management (earthquakes, fires, floods, mine disaster, air crash, et al.), acute sports trauma, acute major trauma, acute toxicity, acute heart disease, and related topics. JAD sets up columns for special subjects in each issue. The journal is aimed at doctors, nurses, paramedics, and ambulance staff. Original scientific researches, reviews, case reports, short communications related to the practice and research of acute diseases are encouraged.
Reviewers of JAD consist of members practicing in different professions from all over the globe. The journal is proud to have such an international and diverse editorial board that will assist and facilitate the publications of articles which reflect a global view on acute disease, as well as emphasizing our focus on supporting the needs of medical practitioners.
As an international journal, JAD is distributed worldwide and welcomes submissions from international contributors and researchers of all specialties. The journal provides a platform for reporting of acute diseases in different settings, which enhances our understanding of course, diagnosis, treatment and clinico-pathologic features of disease. Specialist physicians and general practitioners will find it an indispensable source of reading and reference, and undergraduates will learn a lot from each issue. JAD will allow us to seek opportunities to work with others who share our aim, and to enhance our work through partnership, and to uphold the standards of our profession and contribute to its advancement. We believe that in this way we can contribute to the development of treatment methods of acute diseases and emergency medicine.
President Shunhai Qu
Journal metrics
- Imprint: ELSEVIER


text:
You can stay in Medieval luxury at Leeds Castle
Think you're too good for the wide open spaces that everyday citizens camp on? Then head to Leeds Castle and stay in a village on a one-acre Castle vineyard!
By Rachel Oakley in Cool Travel on Friday 14 August 2015
Think you're too good for the wide open spaces that everyday citizens camp on? Then head to Leeds Castle and stay in a village on a one-acre Castle vineyard!
By Rachel Oakley in Cool Travel on Wednesday 5 August 2015
If you value your life, keep away from England's Poison Garden filled with toxic plants that are so potent, several people pass out last year after inhaling the plants' toxic fumes.
By Perspective in New Art on Friday 15 May 2015
20,000 sheets of poppy red paper and 4 tonnes of stone drawn from the river bed are all that environmental artist Steve Messam is using to create PaperBridge, a stunning intervention into one of Britain's most dramatic landscapes. This remarkable, weight-bearing paper bridge, resplendent in red, has straddled a flowing waterway in the beautiful Lake District as part of Lakes Ignite since early May.
By Sandrine in New Photography on Sunday 15 March 2015
SandJo is a French journalist and photographer living in London who has devoted the past 10 years of her life to shoot the wonderful trees of Hampstead Heath, in North London.
By Rachel Oakley in Cool Travel on Thursday 11 December 2014
Travel to Britain and you'll be treated to more than just good hospitality and rainy days. You'll also be treated to thousands of hilarious village and town names across the island. Names like 'Brown Willy', 'Shag Rock', 'Assycombe Hill', and even 'Beggar's Bush'. And with names like these, why let them go to waste on […]
By Milo Sumner in New Art on Monday 28 July 2014
Banksy, the master of hiding your identity while simultaneously maintaining global fame, has caught the media spotlight once again. Several more of the elusive street artists works have cropped up around The UK, one of which in particular has caused quite a stir.
By Low Lai Chow in New Trends on Tuesday 21 January 2014
Wow, this is way cool: doctors in the UK apparently are now prescribing books to patients with depression. Thanks to a new initiative that debuted in June last year, National Health Service doctors can now prescribe self-help books on slips that patients can take to the library — instead of the pharmacy — to get […]
By Francis Andrews in New Film on Tuesday 1 October 2013
I just got done watching this poignant and beautifully made documentary about the UK's 1970s Northern Soul scene – how all nighters at Wigan's soul clubs bridged a divide between white working class Britain and black America, and became a central focus of life for thousands of disaffected British youths. The programme, presented by journalist […]
By Low Lai Chow in New Trends on Monday 30 September 2013
Yes, it's true. UK's Chessington World of Adventures Resort has hired Animal Print Bouncers to shoo visitors away from entering its premises with animal prints on — or cover up the offensive attire with a grey boiler suit. Apparently, ever since Chessington introduced a safari-style tour that lets visitors get close to the animals, its […]
By Junishi Tsuneoka in New Illustration on Monday 2 September 2013
Once you see Lee Hasler's illustrations, you'll never forget them. His signature parallel perspective style will let you dive into his world of imagination. His character creation is also unique and makes you smile. Hasler, a UK-based illustrator, talks about his style as 'technical yet playful, fun but thoughtful, and I strive to inject charm and personality, into an ever-expanding world of virtual buttons and plastic facades'.
By Annie Churdar in New Products on Saturday 24 August 2013
It's no wonder the next generation of umbrella technology is coming out of the UK. If the stereotype is true, the rain never stops over there. So someone needs to do something about it. According to the team at Rainshader, their revolutionary umbrella design is the next step in evolution for all you sports spectators. […]
By Rebekah Rhoden in New Trends on Monday 15 July 2013
Imagine finding this little guy in your garden. Carol Collen was tending to her garden when she noticed this oddly-shaped strawberry. The British mom couldn't contain her laughter, so of course she showed her family and then immediately took photos to show her friends. Eventually, the funny pictures found their way onto the internet for […]
By Annie Churdar in New Fashion on Monday 17 June 2013
Perhaps you recall Anarchy in the UK by the Sex Pistols from back in the 70s. The song placed 56 on Rolling Stone magazine's list of the 500 Greatest Songs of All Time. So there's that. And here's what's happened all these 40 years later with the rise of the Tumblr generation. I found this hilarious illustration. […]
By Low Lai Chow in Cool Travel on Friday 24 May 2013
Inspired by a magazine that is now accepting nominations to find UK's ugliest new building and award it the Carbuncle Cup, The Guardian recently got its readers to nominate the ugliest architectural structures in the country. Love what one reader said about the Leeds Arena, which is now under construction: 'The desolate car park it […]
By Annie Churdar in Tech on Friday 10 May 2013
Where would 007 be without his special watches, guns, pens, and bombs? We all know that James Bond would only be half the super spy he is without all those gadgets Q outfits him with. Take a gander at this website for a rundown of every gadget the agent has ever used. Categorized by movie and use, each clever invention […]
by Kenny Ong
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Alabama will play home-and-home games against Auburn, Kentucky, South Carolina, Texas A&M and Vanderbilt, as the Southeastern Conference unveiled the 2015 men's basketball composite league schedule on Friday.
Click here for the original story.
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Gurnee Hotel & Suites
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- Continental Breakfast
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New York, New York
... Well we took the easy way out and caught a cab!!!! This little west African guy got us into manhattan in no time!! We just had to close our eyes!!!! Our hotel is only a block away from Times Square, so once we were settled found bar, few drinks, dinner then went to see if Times Square had changed!!!! Apart from quite a few Renos still quite spectacular!! See ...
Flights Closed
Well yesterday we arrived at the airport at what I perceived to be plenty of time to board our flight. Once at the counter, we were informed that my perception was slightly skewed, and the flight was closed. The clerk at the counter made it seem as if it was not a big deal and gave us a number to reservations to be re-booked on a later flight. From that point it was ...
Roll Doll and Faye
... like the inner city man who had created "Pimp Oil" to freshen up the interior of your vehicle, and the fellow who pitched a new shipping company that would send all packages from a central location in Memphis. He was even offered a percentage of the business, but they turned them both down, only to watch FedEx become - well ...
Northwestern (and other various enjoyments)
... the classrooms are authentic and old fashioned while still equipped with the latest in technology. We visited the student union, walked through the quads, and saw the famous women's lacrosse team practicing. It was a nice afternoon!
After Evanston we hopped back into the minivan and drove...a lot. We stopped at some outlet malls to buy me some sneakers (my favorite shoes had worn a big hole in them) and then back into the van ...
Depth over distance everytime, my dear.
... you listen to when taking mini roadtrips) the cheesy Moulin Rouge soundtrack was playing through my speakers, so as all this was infiltrating our vision we were being serenaded by my stereo telling us 'We could be heroooooes' and yeah.. it pretty much lived up to the hype that had been set.
And this was before we'd even gotten out of the car.
Walking around that place was simply a whole other dimension of magnificence. A ...


text:
Shop Sections
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Portland, Oregon,
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Opened on Jul 14, 2008
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Lampworked Artisan Bracelet Beads by Kathy Perras
Welcome to my Etsy Shop. You will find my newest Troll bracelet bead designs as well as my older designs. If you don't see what you are looking for, send me a message to see if I have a particular design in stock or if one could be made for you. I take studio orders in the order that they are received and ship worldwide.So feel… read more
This shop accepts Etsy Gift Cards.


text:
These days, we only call it propaganda when despotic North Korean leaders visit their troops.
ONE News Political Editor Corin Dann was with John Key as he personally saw the conditions New Zealand troops are living in at Camp Taji.
The Labour Party is threatening to overwrite parts of the deal.
In Mike's opinion the signing of the TPP is a win for NZ.
Wine, beef, milk and medicine. Tim Wilson explains how these necessities will be hit by the TPP - and what that means for you.
Political Reporter Katie Bradford takes a look at what the deal involves and will give New Zealand.
Labour's acting leader was discussing the TPP agreement, which Tim Groser was negotiating.
Peter and Sylvia Aichison were upset when a fort interrupted their spectacular view over Wellington.
The inquiry into Smith's escape to Brazil has found several shortcomings by the Department of Corrections, Police, and Customs.
Foreign Minister Murray McCully has met Australia's Foreign Minister Julie Bishop to discuss the deportation of Kiwis living across the Tasman.
Tolley is standing by her controversial comments about state care and parenthood.
Increasing numbers of New Zealanders are being held in prison before being sent back here.
John Key has met with the Japanese PM, and will meet with Barack Obama tomorrow.
"I think we need to be getting in there with better contraception and family planning advice," the minister says.
US-Russian relations deteriorated significantly after Russia annexed Crimea from Ukraine in March 2014.
"Anybody taking a bit of a glance would know that off-the-shelf is not something I regularly purchase."
The New Zealand First leader accuses the prime minister of reneging on an assurance Red Peak wouldn't be included in November's first flag referendum.
Australia's new Prime Minister has unveiled a package of measures to tackle domestic violence.
James Shaw told Breakfast the Greens' bill was in response to the "significant" public support for Red Peak.
Parliament has been in urgency to get Red Peak into the November referendum.
A Bill adding it as a fifth option passed its first reading in Parliament tonight.
'Coming to NZ is a privilege, you come if you have something to contribute or if you're very, very desperate.'
Government rules reduction taskforce is seeking to make life easier for New Zealanders.
The call comes after concerns were raised by a Far North trust who feel they'll lose their charitable status.
Ioane Teitota's bid to be a climate change refugee has failed but the PM says in future NZ may have to take refugees from the Pacific.
While National may have successfully negotiated year one of this term, the next looks far more challenging. Our Political Editor Corin Dann explains why.
Australia's new PM led an unsuccessful 1999 referendum to replace the Queen with a president as the country's head of state.
Trump started off with a bang, but was quickly attacked by his fellow candidates.
Opponents say a petition to keep Wellington's quirky Kate Sheppard crossing lights was a publicity stunt.
John Key is standing his ground and said if Red Peak is not added it'd be the "sole fault" of Andrew Little.
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