US3736043A - Electrochemical molecular display and writing - Google Patents

Electrochemical molecular display and writing Download PDF

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Publication number
US3736043A
US3736043A US00128833A US3736043DA US3736043A US 3736043 A US3736043 A US 3736043A US 00128833 A US00128833 A US 00128833A US 3736043D A US3736043D A US 3736043DA US 3736043 A US3736043 A US 3736043A
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electrodes
electrode
compound
electrolyte
electrochemical
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US00128833A
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C J Sambucetti
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International Business Machines Corp
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International Business Machines Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1506—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode

Definitions

  • the apparatus DISPLAY AND WRITING includes a substrate carrying highly reflective display electrode strips which can be electrically addressed [75] Inventor: Carlos sambucem Mohegan selectively to present characters. Characters are dis- Lake played by producing a cloud of iodine molecules ob- [73] Assignee: International Business Machines scuring certain electrode segments or strips composed Corporation, Armonk, N .Y. of a noble metal or the like normally visible through a transparent cover in the absence of an iodine cloud.
  • the electrolyte 3 includes pentavalent nitrogen iodides with a radical 1 5 References Cited selected from the choline group such as acetylcholine, propionylcholine and butyrylcholine iodides.
  • an object of this invention is to provide an electrochemical display method and device in which the electrodes do not react with the electrolyte and are not plated but with which an optical effect is provided by electrochemical means.
  • Another object of this invention is to provide an electrochemical display or sign which exhibits memory and which provides a high quality display with long life and a corresponding method.
  • Still another object of this invention is to provide an electrode structure which is economical and which employs a minimum of noble metal material without bleeding of a base metal through a noble metal material layer which is used as the display electrode.
  • an electrochemical display apparatus including a pair of electrodes, one of said electrodes including a surface composed of a noble metal selected from gold, platinum, iridium and rhodium, and an electrolyte providing a reversible reduction-oxidation reaction providing a change in the reflection characteristics in connection with the one electrode.
  • the electrolyte comprises an organic polar iodide compound selected from the group including ammonium, arsonium, and phosphonium compounds.
  • the electrolyte is a pentavalent nitrogen compound of the general formula where R,, R,, R,, and R are selected from hydrogen, alkyl, and aromatic groups which can be simple and substituted.
  • the choline groups can be selected from acetylcholine, propionylcholine and butyrylcholine iodides, and electrolyte concentration varies from 0.5 to 20 percent by weight in water, and the electrolyte concentration is approximately 2.5 percent by weight in water.
  • a soluble, non-reactive material is added to the electrolytic solution for retarding motion of substances in the electrolyte, which can be gelatine added to the electrolytic solution in sufficient concentration to increase viscosity.
  • a soluble, non-reactive material is added to the electrolytic solution for retarding motion of substances in the electrolyte, which can be gelatine added to the electrolytic solution in sufficient concentration to increase viscosity.
  • the other of the q electrodes comprises a reference electrode composed of silver and silver iodide.
  • radiation reflection is controlled by apparatus including a pair of electrodes. At least one of the electrodes has a surface adapted for reflection of radiation. The surface is composed of an inactive substance. Electrical terminals are connected to said electrodes. An electrolyte provides a reversible reductionoxidation reaction to produce at the one electrode (when current flows between said electrodes in one direction) a reaction product having an optical characteristic of absorbing light to a substantial degree when adjacent to the one electrode. A container holds the electrodes and the electrolyte.
  • FIG. 1 shows a perspective view of a display device constructed in accordance with this invention.
  • FIG. 2 shows a vertical section taken along line 2-2 in-FIG. 1.
  • FIG. 3 shows a section taken along line 3-3 in FIG. 2 of the display device of FIGS. 1 and 2'connected in an electrical circuit for providing a display of various alphanumeric characters.
  • FIG. 4 is an writing apparatus embodying this invention.
  • an electrochemical display device 10 includes a plurality of anodes 11-17, composed of a gold surface over a layer of palladium upon a layer of copper on a printed circuit board 18. The copper had been etched to form separate display electrodes before palladium and gold were added. A transparent cover 19 composed of glass or lucite, and a gasket 20 between the board 18 and the cover 19 are included. An electrolyte 21 is contained within the space enclosed by the cover 19, the gasket 20 and the board 18.
  • the electrolyte 21 comprises an agugt us r wateralcohol solution of organic iodide compound, picfe rably one of the pentavalent nitrogen compounds in which iodine is attached to the nitrogen as follows:
  • the compound should be highly soluble in water.
  • the preferred choice of an electrolyte comprises acetylcholine iodide or propionylcholine iodide preferably having a weight concentration in water of 2 to 6 percent.
  • the iodide film has a strong covering power on the surface of the display electrodes 11-17 and does not show any bleeding effects. Bleeding refers to rapid visible migration of the iodine molecules away from the strip 11-17. Wetting enhances both resolution, where one is writing characters with iodine, and memory, because line with is not spread and dispersal is slower.
  • the cathodic reaction at reference electrodes 23, 24 and 25 consists in the discharge of an alkyl ammonium cation which prevents hydrogen gas evolution, if the voltage is kept below l.5 volts.
  • the display electrode segments 11-17 (anodes) assume a dark brown color, whereas-the reference electrodes (cathodes) retain their usual color although they are not visible, in any event.
  • the polarity of the cell is reversed by switches 41-47, the film at the electrodes 11-17 vanishes in the solution and it is formed again at the reference electrodes 23, 24 and 25.
  • the process can be repeated many times without affecting the conditions of pure gold surface of display segments 11-17 at all.
  • the noble metal does not participate in the reaction and acts only as an interface for electron 4 exchange between the external circuit ahd ions in solution.
  • the display electrodes 11-17 can be manufactured by electrochemically etching a printed circuit board to form the underlying electrode structure and perform an additional step of etching with acid in such a manner as to produce small pockets or holes in the surface. Then the palladium can be added by electrodeposition and then the gold can be deposited to yield correspondlO ing plated pockets in which iodine film will be trapped for longer periods of time to lengthen memory.
  • the electrode reactions for the build up and erasing of the film are:
  • the electrolyte system consists of a certain amount of l" ni-ry-m dissolved in water.
  • R R R and' R can be either alifatic (methyl, ethyl, etc.) or aromatic groups (phenyl, benzoyl groups) either the same or different.
  • phenyl, benzoyl groups either the same or different.
  • trimethyl-phenyl ammonium iodide and dimethylethyl-benzoyl ammonium iodide work reasonably well.
  • wateralcohol or other solvent mixtures v
  • acetylcholine and propionylcholine iodides are excellent, especially when the aqueous concentration is maintained between two to 6 grams percent.
  • Acetylcholine Iodide Legend The simplest compound of pentavalcnt nitrogen is one of which all R groups are hydrogen, which is ammonium iodide Ill ll--lTl ll 1- This compound works in the cell'and the free iodine forms at the anode (writing) and erases when the display segment 11-17 is made a cathode. However, the
  • choline group as one of the radicals of the pentavalent nitrogen formulation, is possible with varying complexity of the substituted choline molecule.
  • Acetylcholine iodide, propionyl choline iodide, butyrylcholine iodide and benzoylcholine iodide cause the electrolyte to be a very efficient wetting agent and the brown film produced upon writing remains strongly attached to the character surface of the electrode 11-17.
  • Acetylcholine iodide and propionylcholine iodide electrolytes are operative within a temperature ,mn ge from 0C to 85C although memory is poor at the higher temperature due to the high energy level of the iodine molecules.
  • the optimum temperature range for these two electrolytes is l0C at which the electrolyte tends to gell and 50C at which the electrolyte evaporates and memory deteriorates.
  • the pentavalent nitrogen choline compounds are satisfactory in mixtures in which the solvent is a solvent such as methanol, ethanol, ace tone, D.M.S.O.
  • the solvent is a solvent such as methanol, ethanol, ace tone, D.M.S.O.
  • Pentavalent nitrogen compounds -with iodide produce a good writing and erasing display effect. This occurs in pure aqueous solutions or in water-solvent mixtures. Compounds containing the choline group are most suitable because bleeding of the film disappears and the duration of the memory is much enhanced. 11.
  • Other iodide compounds without pentavalent nitrogen Simple inorganic iodides (potassium iodide, lithium iodide, lanthanum iodide, etc.), show poorer film adherence and memory and a great deal of gas evolution.
  • Organic compounds in which nitrogen is substituted by arsenic such as methyl-tri-phenyl arsonium iodide do not dissolve in water. Water-alcohol mixtures of this compound did show a poorer reversible writingerasing effect.
  • Methyl triphenyl phosphonium iodide shows considerable hydrolysis decomposition. Besides arsenic and phosphonium compounds, other compounds containing sulfur instead of nitrogen such as ethyl-methyl sulfonium iodide, yield poor results.
  • Acetylcholine iodide or propionylcholine iodide give excellent results.
  • a concentration of 2.5 grams of acetylcholine iodide in l00 grs. of water gives fast speed with a memory duration of less than 1 minute.
  • gelatin is added to the solution. The
  • gelatin is not critical. A concentration of 1 percent grams of gelatin increases the memory to about 5 minutes, but the solution is still fluid. A concentration of 10 grams percent of gelatin allows working with a solid electrolyte.
  • Iodine migration studies indicate that the percentage loss of iodine is linear during the first 20 seconds, then the curve flattens out and total migration occurs after 3 minutes. In the first 20 seconds, the percentage loss is approximately 0.5 percent per second. As a display for a card punch verifier, a very fast operator can punch and verify an column card in about 20 seconds, thus producing roughly 10 character/8 hour day.
  • the cell reference electrode can be a gold barplaced alongside or around the gold-plated character.
  • the problems associated with this are that when writing iodine on a character at voltages over L5 (to obtain faster writing) gas is evolved at the gold reference. Also, when erasing a character, the iodine film is transferred to the gold reference thus allowing far more iodine migration and dispersion in the electrolyte.
  • Substitutes for a gold reference electrode of a different material include aluminum metal, which during the character erasing cycle is superior because the iodine film erased from the gold character does not reform on the aluminum surface. During the writing cycle, gas evolution occurs on the aluminum reference as it does no gold.
  • a reversible reference electrode which acts as a carrier and reservoir for iodide ions is the silver, silver iodide electrode shown in the preferred embodiment.
  • the element is simply made of silver surface which is coated with a crystal layer of silver iodide. The coating is applied by electrolysis in the same acetylcholine iodide electrolyte.
  • the mechanism for writing and erasing with this reference electrode is:
  • Electrochemical displays permit patterns of information to be presented in sizes as small as fractions of an inch in character size to several inches in character size. They also permit the display system to be operated a.
  • the silver, silver iodide electrode allows writing low applied voltages which are compatible with semiconductor or transistor circuits.
  • the reversible writing process in these cells consists in the electrical generation of sufficient iodine to form a character.
  • the film In the erasing process the film is electrically reduced back to iodide. lffdbring the interval between writing and erasing there were no exchange between the film and the solution, all the iodine film produced on writing would be electrically recovered by erasing and the solution would last indefinitely.
  • molecular iodine is soluble in solutions of iodide (which is the main ion in the electrolyte) and, therefore, when the film is deposited and the character is left on, there is a gradual process of migration of the molecules from the film to the solution.
  • This phenomenon produces two effects; (a) the film tends to vanish with time even without electrical erasing, so that memory is limited. This is not a critical limitation because memory times of up to thirty minutes are easily achieved. (b) this dissolution of the iodine film by interaction with iodide from the electrolyte forms an iodine-iodide complex in which part of the iodine is in free form and therefore no longer available for writing.
  • Such displays permit the use of arrays of characters made by photoetching as is done in connection with printed circuits.
  • a dot raster form of character can be provided by means of providing large numbers of dots connected by means of arrays of horizontal and vertical conductors. Such displays are flat.
  • An application of this type of technology is that a keyboard may be used to enter the data upon the display, and then, if the display includes memory, the computer system may extract the data from the memory in the display and erase the display at the same time.
  • FIG. 4 Another embodiment of this invention is shown in FIG. 4.
  • the above electrochemistry can be applied to printing upon a paper 50 (or other similar material) impregnated with one of the above suggested electrolytes, with a writing electrode 51 on one side of the paper 50 and a reference electrode 52 on the other side of the paper 50 so that iodine molecules can form in the paper at the noble metal electrode 51 in an electrochemical printer which employs electrodes in direct contact with the paper 50.
  • Switch 53 connects the electrodes in circuit with batteries 54 and 55 which provide currents in reverse directions for writing and erasing.
  • the printed circuit board 18 is the same color as the surface of the display segments 11-17, then when the iodine cloud or film is formed upon the segments, it will write a line rather than obscuring one. In essence, then one can write white on black or black on white.
  • An electrochemical data presentation apparatus including:
  • one of said electrodes comprising a data presentation electrode including a noble metal selected from gold, platinum, iridium and rhodium,
  • a fluid medium for selectively obscuring said data presentation electrode from view said medium containing an electrolytic compound providing an electrochemical reversible reduction-oxidation reaction product composed of free molecules of an .anion changing the lighttransmitting characteristics of said medium as a function of the proportion of said compound comprising said reaction product, p d. a container holding said electrodes and said medium containing said electrolytic compound,
  • reaction product being suspended in said fluid medium.
  • An electrochemical data presentation apparatus including:
  • one of said electrodes comprising a data presentation electrodes including a noble metal selected from gold, platinum, iridium and rhodium,
  • a medium for presentation of indicia said medium containing an electrolytic compound providing an electrochemical reversible reduction-oxidation reaction product changing the transmission characteristics of said medium
  • An electrochemical data presentation apparatus including:
  • one of said electrodes comprising a data presentation electrode including a noble metal selected from gold, platinum, iridium and rhodium,
  • said electrolytic compound comprising a pentavalent nitrogen compound of the general formula where R,, R R and R, are selected from hydrogen, alkyl, and aromatic groups including both simple and substituted forms.
  • choline groups are selected from acetylcholine, propionylcholine and butyrylcholine iodides.
  • An electrochemical data presentation apparatus including:
  • one of said electrodes comprising a data presentation electrode including a noble metal selected from gold, platinum, iridium an rhodium,
  • a medium for presentation of indicia said medium containing an electrolytic compound providing an electrochemical reversible reduction-oxidation reaction product changing the transmission characteristics of said medium
  • An electrochemical data presentation apparatus including:
  • one of said electrodes comprising a data presentation electrode including a noble metal selected from gold, platinum, iridium and rhodium,
  • a medium for presentation of indicia said medium containing an electrolytic compound providing an electrochemical reversible reduction-oxidation re action product changing the transmission characteristics of said medium
  • said one electrode including a basic layer of copper supported upon a substrate, an intermediate layer of palladium and an outer layer of gold.
  • Apparatus in accordance with claim 2 wherein the other of said electrodes comprises a reference electrode composed of silver and silver iodide.
  • An electrochemical radiation reflection controlling apparatus including:
  • At least one of said electrodes having a light reflecting surface, said surface being composed of an inactive substance
  • an electrolytic fluid comprising means for provid ing a reversible reduction-oxidation reaction to produce at said one electrode, when current flows between said electrodes in one direction a reaction product composed of free molecules of an anion having an optical characteristic of absorbing light directed towards said electrode to a substantial degree when said reaction product is suspended in said fluid adjacent to said one electrode,
  • An electrochemical reflection controlling device including:
  • a display device including a. a pair of sets of electrodes, one set of electrodes comprising a printed circuit board including an etched copper pattern of electrode structures plated with palladium and then plated with gold,
  • An electrochemical display apparatus including:
  • one of said electrodes including a noble metal with high reflection characteristics selected from gold, platinum, iridium and rhodium,
  • An electrochemical data presentation method including:
  • Electrodes including a noble metal selected from gold, platinum, iridium and rhodium as a data presentation electrode,
  • a method in accordance with claim 17 including employing as said electrolyte an organic polar iodide compound selected from the group including ammonium, arsonium, and phosphonium compounds.
  • a method in accordance with claim 17 including employing as said electrolyte a pentavalent nitrogen compound of the general formula 12 where R R R and R a e selected from hydrogen, alkyl, and aromatic groups which can be simple and substituted.
  • An electrochemical radiation reflection controlling apparatus including:
  • At least one of said electrodes comprising a display electrode having a surface adapted for reflection of radiation, said surface being composed of gold,
  • said one electrode including a basic layer of copper supported upon a substrate, an intermediate layer of palladium and an outer layer of gold, said palladium being electrodeposited upon the copper base, said gold being plates upon said palladium, the other of said electrodes comprising a reference electrode composed of silver and silver iodide,
  • an electrolyte said electrolyte being a pentavalent nitrogen compound of the genera formula where R R R and R are selected from hydrogen, alkyl, and aromatic groups which can be simple and substituted, said choline groups being selected to form acetylcholine, propionylcholine and butyrylcholine iodides, including a solvent containing water to form an electrolytic solution,
  • said electrolyte comprising means for providing a reversible reduction-oxidation reaction to produce at said one electrode for current between said electrodes in one direction, a reaction product having an optical characteristic of absorbing light to a substantial degree when adjacent to said one electrode,
  • a soluble, non-reactive material including gelatin being added to said electrolytic solution for retarding motion of substances in the electrolyte to increase viscosity

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
US00128833A 1971-03-29 1971-03-29 Electrochemical molecular display and writing Expired - Lifetime US3736043A (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950077A (en) * 1974-09-20 1976-04-13 Texas Instruments Incorporated Lead reference and counter electrode for an electrochromic display
US3961842A (en) * 1974-09-20 1976-06-08 Texas Instruments Incorporated Regenerating electrode for electrochromic display cell
US4070663A (en) * 1975-07-07 1978-01-24 Sharp Kabushiki Kaisha Control system for driving a capacitive display unit such as an EL display panel
US4074256A (en) * 1975-08-20 1978-02-14 Citizen Watch Company Limited Driver circuit for driving electrochromic display device
DE2752191A1 (de) * 1976-12-06 1978-06-08 Philips Corp Elektrophoretische bildwiedergabevorrichtung
US4114890A (en) * 1975-07-15 1978-09-19 Nippon Kogaku K.K. Reproduction apparatus for a game
EP0000616A1 (en) * 1977-06-29 1979-02-07 International Business Machines Corporation Matrix addressable electrochromic display device
JPS5446546U (OSRAM) * 1977-09-07 1979-03-31
US4149146A (en) * 1976-02-09 1979-04-10 Citizen Watch Company Limited Driver circuit for electrochromic display device
US4210909A (en) * 1977-04-20 1980-07-01 Sharp Kabushiki Kaisha Complete bleaching of non-selected display electrodes in an electrochromic display drive
DE3048985A1 (de) 1979-12-24 1981-09-17 Sharp K.K., Osaka Elektrochromische darstellungsvorrichtung
US4297696A (en) * 1979-04-24 1981-10-27 Sharp Kabushiki Kaisha Color uniforming drive in an electrochromic display device
US4300138A (en) * 1976-12-17 1981-11-10 Sharp Kabushiki Kaisha Electric memory detector in an ECD driver
US4311361A (en) * 1980-03-13 1982-01-19 Burroughs Corporation Electrophoretic display using a non-Newtonian fluid as a threshold device
US6120518A (en) * 1998-04-01 2000-09-19 Promex, Inc. Non-reflective surfaces for surgical procedures
US11221536B2 (en) * 2016-03-28 2022-01-11 Panasonic Intellectual Property Management Co., Ltd. Electrochromic device

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2407746A1 (fr) * 1977-11-07 1979-06-01 Commissariat Energie Atomique Electrode pour cellule d'electrolyse, notamment pour cellule d'affichage electrolytique et son procede de fabrication
US4264693A (en) * 1978-12-29 1981-04-28 International Business Machines Corporation Light and current sensitive film and print-display system therewith
FR2505067A1 (fr) * 1981-04-30 1982-11-05 Jaeger Cellule d'affichage electrolytique a lame arriere transparente

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US16733A (en) * 1857-03-03 Screw-wren-ch
US3096271A (en) * 1958-11-26 1963-07-02 Burroughs Corp Data display device
US3153113A (en) * 1961-01-26 1964-10-13 Eastman Kodak Co Electroplating light valve
US3190177A (en) * 1958-04-15 1965-06-22 Edward K Kaprelian Electrochemical shutters
US3280701A (en) * 1961-09-05 1966-10-25 Donnelly Mirrors Inc Optically variable one-way mirror
US3282160A (en) * 1963-01-07 1966-11-01 Dow Chemical Co Color reversible electrochemical light filter utilizing electrolytic solution
US3303488A (en) * 1963-02-11 1967-02-07 Electroscope Res Inc Electro-optic information display device utilizing an acid-base indicator
US3443859A (en) * 1964-03-09 1969-05-13 Polaroid Corp Variable light-filtering device
US3451741A (en) * 1966-06-15 1969-06-24 Du Pont Electrochromic device

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Publication number Priority date Publication date Assignee Title
US16733A (en) * 1857-03-03 Screw-wren-ch
US3190177A (en) * 1958-04-15 1965-06-22 Edward K Kaprelian Electrochemical shutters
US3096271A (en) * 1958-11-26 1963-07-02 Burroughs Corp Data display device
US3153113A (en) * 1961-01-26 1964-10-13 Eastman Kodak Co Electroplating light valve
US3280701A (en) * 1961-09-05 1966-10-25 Donnelly Mirrors Inc Optically variable one-way mirror
US3282160A (en) * 1963-01-07 1966-11-01 Dow Chemical Co Color reversible electrochemical light filter utilizing electrolytic solution
US3303488A (en) * 1963-02-11 1967-02-07 Electroscope Res Inc Electro-optic information display device utilizing an acid-base indicator
US3443859A (en) * 1964-03-09 1969-05-13 Polaroid Corp Variable light-filtering device
US3451741A (en) * 1966-06-15 1969-06-24 Du Pont Electrochromic device

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961842A (en) * 1974-09-20 1976-06-08 Texas Instruments Incorporated Regenerating electrode for electrochromic display cell
US3950077A (en) * 1974-09-20 1976-04-13 Texas Instruments Incorporated Lead reference and counter electrode for an electrochromic display
US4070663A (en) * 1975-07-07 1978-01-24 Sharp Kabushiki Kaisha Control system for driving a capacitive display unit such as an EL display panel
US4114890A (en) * 1975-07-15 1978-09-19 Nippon Kogaku K.K. Reproduction apparatus for a game
US4074256A (en) * 1975-08-20 1978-02-14 Citizen Watch Company Limited Driver circuit for driving electrochromic display device
US4149146A (en) * 1976-02-09 1979-04-10 Citizen Watch Company Limited Driver circuit for electrochromic display device
DE2752191A1 (de) * 1976-12-06 1978-06-08 Philips Corp Elektrophoretische bildwiedergabevorrichtung
US4300138A (en) * 1976-12-17 1981-11-10 Sharp Kabushiki Kaisha Electric memory detector in an ECD driver
US4210909A (en) * 1977-04-20 1980-07-01 Sharp Kabushiki Kaisha Complete bleaching of non-selected display electrodes in an electrochromic display drive
EP0000616A1 (en) * 1977-06-29 1979-02-07 International Business Machines Corporation Matrix addressable electrochromic display device
JPS5446546U (OSRAM) * 1977-09-07 1979-03-31
US4297696A (en) * 1979-04-24 1981-10-27 Sharp Kabushiki Kaisha Color uniforming drive in an electrochromic display device
DE3048985A1 (de) 1979-12-24 1981-09-17 Sharp K.K., Osaka Elektrochromische darstellungsvorrichtung
DE3050781C2 (de) * 1979-12-24 1985-04-04 Sharp K.K., Osaka Elektrochrome Darstellung
US4311361A (en) * 1980-03-13 1982-01-19 Burroughs Corporation Electrophoretic display using a non-Newtonian fluid as a threshold device
US6120518A (en) * 1998-04-01 2000-09-19 Promex, Inc. Non-reflective surfaces for surgical procedures
US11221536B2 (en) * 2016-03-28 2022-01-11 Panasonic Intellectual Property Management Co., Ltd. Electrochromic device

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FR2131993A1 (OSRAM) 1972-11-17
DE2213506A1 (de) 1972-10-05
FR2131993B1 (OSRAM) 1979-08-10
GB1381394A (en) 1975-01-22

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