WO1986006179A1 - Application of the electrolytic process to change the degree of reflection of mirrors - Google Patents

Application of the electrolytic process to change the degree of reflection of mirrors Download PDF

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Publication number
WO1986006179A1
WO1986006179A1 PCT/DE1986/000104 DE8600104W WO8606179A1 WO 1986006179 A1 WO1986006179 A1 WO 1986006179A1 DE 8600104 W DE8600104 W DE 8600104W WO 8606179 A1 WO8606179 A1 WO 8606179A1
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Prior art keywords
mirror
electrode
viewer
facing
layer
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PCT/DE1986/000104
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German (de)
French (fr)
Inventor
Peter Knoll
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Robert Bosch Gmbh
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Publication of WO1986006179A1 publication Critical patent/WO1986006179A1/en

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
    • B60R1/02—Rear-view mirror arrangements
    • B60R1/08—Rear-view mirror arrangements involving special optical features, e.g. avoiding blind spots, e.g. convex mirrors; Side-by-side associations of rear-view and other mirrors
    • B60R1/083—Anti-glare mirrors, e.g. "day-night" mirrors
    • B60R1/088—Anti-glare mirrors, e.g. "day-night" mirrors using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase

Definitions

  • DE-PS 19 48 362 proposes continuously changing the absorption of an electrochromic layer, which is located between the viewer and a reflector, by applying a voltage to two electrodes that enclose the electrochromic layer. Although this level meets the legal requirements (5% ⁇ R ⁇ 55%), the switching times are in the order of several seconds and are therefore unreasonably long.
  • DE-OS 29 34 451 a dimmable rearview mirror has also become known, which uses a liquid crystal cell of the twisted nematic type (TN-LCD) between crossed polarizers. Since polarizers absorb approx. 50% of the incident light, legal requirements are difficult to meet. Typical values for the reflectance of such mirrors are 7% ⁇ R ⁇ 3T%.
  • An LCD rearview mirror developed by Murakami Kameido (Japan) does not need polarizers.
  • dye molecules are embedded as light absorbers, which can be folded from a non-absorbent layer into an absorbent layer by applying an electric field. The efficiency of this mirror is poor. According to the manufacturer, it is 27% ⁇ R ⁇ 51%.
  • Motor vehicle rear-view mirrors, the reflectance of which can be changed by means of discolourable or color-neutral liquid crystal layers in conjunction with polarization filters, are also described in DE-OSes 29 48 514, 31 44 143 and 33 02 195.
  • EP-A 0 006 811 discloses an electrolytic cell which has a transparent electrode and a metallic counter electrode, between which an electrolyte is located. Depending on the polarity of a voltage applied to the two electrodes, a layer of the metal of the metallic electrode is deposited on the transparent electrode or detached therefrom.
  • the cell serves as a display device for displaying symbols, numbers and letters.
  • the proposed use of the electrolysis method for producing and detaching a reflective metal layer on a flat electrode by reversing the current flow in the electrolyte in a mirror, in particular in a rear view mirror for motor vehicles provides the advantage that such a mirror reacts very quickly to polarity reversal of the voltage, so that there are short fade-in and fade-in times.
  • it fulfills the legal requirements with regard to reflectivity in light and dark states, whereby the achievable contrasts are higher than with the previously known dimmable mirrors.
  • the mirror does not require polarizers and can be made with commercially available materials.
  • reflecting metal is preferably detached from a front electrode facing the viewer and deposited on a rear electrode of the mirror.
  • Another method which simplifies the layer structure consists in that, in order to reduce the reflectivity, reflective metal is detached from a rear electrode and deposited in granular form on a front electrode of the mirror facing the viewer.
  • the mirror itself can have two flat electrodes that can be connected to a polarity-reversible voltage source, each of which is arranged on a support plate enclosing the electrolyte, the front electrode facing the viewer and the support plate being made of transparent materials, while the rear electrode is made of a reflective metal is.
  • FIG. 1 shows the electrolytic cell of a dimmable mirror in a perspective view
  • FIG. 2 shows a section through the cell shown in FIG. 1 with electrical wiring.
  • the upper carrier plate 1 consists of a transparent material, preferably of glass. Glass is also preferably used as the material for the lower carrier plate 3.
  • an active electrode 4 made of transparent material, preferably of tin-indium oxide.
  • a counter electrode 5 made of reflective metal, for example silver or aluminum, is applied to the inside of the lower carrier plate 3.
  • the carrier plate arrangement 1, 3 is hermetically sealed all around at the edges. The spacing of the plates from one another is adjusted to the required dimension between 100 ⁇ m and 200 ⁇ m via a frame 6. The volume created in this way between the two carrier plates is filled with an electrolyte 7.
  • the metal layer serving as counter electrode 5 is coated with an insulating layer 8 which is permeable to charge carriers.
  • This layer is preferably colored black to improve the anti-glare effect. It is expediently designed as a porous film layer with a thickness of 0.1 to 0.5 mm.
  • PTFE, polypropylene or polyethylene can be used as the layer material.
  • the voltage of a battery 11 is applied to the electrodes 4, 5 by means of the changeover switch 10 with such polarity that a metal layer 12 (FIG. 1) made of metal is applied to the electrode 5 by the electrolytic process that is now starting the electrolyte 7 is deposited on the originally transparent electrode 4.
  • a metal layer 12 made of metal is applied to the electrode 5 by the electrolytic process that is now starting the electrolyte 7 is deposited on the originally transparent electrode 4.
  • the reaction follows the scheme:
  • the metal layer 12 deposited on the active electrode 4 has the appearance and the effect of a metallic mirror, the reflectivity of which depends on the reflectance of the deposited metal.
  • the reflectance for silver layers is between 0.90 and 0.94 and for aluminum layers between 0.80 and 0.85.
  • Other suitable reflection layers are tin layers, zinc layers, nickel layers and platinum layers, the degree of reflection of which, however, is lower than that of silver and aluminum layers.
  • An electrolyte suitable for depositing a highly reflective silver layer on the electrode 4 connected as the cathode can consist, for example, of a highly dilute nitric acid containing silver nitrate.
  • Another electrolyte composition (AgJ + UaJ in methanol) allows a reversal of the function described above as follows:
  • a mirror layer made of silver is applied to the carrier plate 3 as the electrode 5.
  • the insulation layer 8 is omitted.
  • the light emitted by the light source 9 penetrates the transparent electrolyte 7 and is reflected by the mirror layer 5 into the eye 2 of the viewer.
  • silver is deposited on the electrode 4 at a current density of 20 to 25 A / cm 2 of such granularity that it appears black and thus absorbs incident light.
  • the absorption of such silver layers with a thickness of 500 nm to 1.5 ⁇ m is very high.
  • the separation takes place at voltages of the order of 1 V in 50 to 200 ms.

Abstract

Through the production and removal by means of electrolysis of a reflecting metal layer (12) on a flat electrode (4), the degree of reflexion of a mirror, in particular a rear view mirror for vehicles, can be changed in a reversible manner.

Description

Anwendung des Elektrolyseverfahrens zum Verändern des Reflexionsgrades von SpiegelnApplication of the electrolysis process to change the reflectance of mirrors
Stand der TechnikState of the art
Es gibt seit langem abblendbare Rückspiegel für Kraftfahrzeuge, bei denen, eine optisch aktive Scheibe innerhalb des Spiegels kippbar angeordnet ist und durch einen Kippmechanismus in eine von zwei vorgegebenen Lagen gekippt werden kann. In der einen Stellung der Scheibe wird praktisch das gesamte, auf den Spiegel fallende Licht reflektiert, so daß ein helles Bild entsteht. In der zweiten Stellung gelangt dagegen nur ein abgeschwächtes reflektiertes Bild in das Auge des Beschauers, wodurch die Blendgefahr herabgesetzt wird. Solche mechanischen Konstruktionen sind relativ aufwendig und nicht bedienerfreundlich. Es ist auch schon bekannt, Spiegel "elektronisch" abzublenden. Hierzu wird in der DE-PS 19 48 362 vorgeschlagen, die Absorbtion einer elektrochromen Schicht, die sich zwischen dem Beschauer und einem Reflektor befindet, durch Anlegen einer Spannung an zwei, die elektrochrome Schicht einschließenden Elektroden kontinuierlich zu verändern. Dieser Spiegel erfüllt zwar die gesetzlichen Auflagen (5 %≦ R ≦55 % ) , jedoch liegen die Schaltzeiten in der Größenordnung von mehreren Sekunden und sind damit unzumutbar lang. Durch die DE-OS 29 34 451 ist ferner ein abblendbarer Rückspie¬gel bekanntgeworden, der eine Flüssigkristallzelle vom verdrillt nematischen Typ (TN-LCD) zwischen gekreuzten Polarisatoren benutzt. Da Polarisatoren ca. 50 % des einfallenden Lichts absorbieren sind gesetzliche Auflagen nur schwer zu erfüllen. Typische Werte für den Reflexionsgrad solcher Spiegel sind 7 %≦ R ≦ 3T % . Ein von der Firma Murakami Kameido (Japan) entwickelter LCD-Rückspiegel kommt ohne Polarisatoren aus. In dem Flüssigkristall sind als Lichtabsorber Farbstoffmoleküle eingebettet, die durch Anlegen eines elektrischen Feldes von einer nicht absorbierenden Lage in eine absorbierende Lage umgeklappt werden können. Der Wirkungsgrad dieses Spiegels ist schlecht. Er liegt nach Herstellerangaben bei 27 %≦ R≦ 51 %. Kraftfahrzeugrückspiegel, deren Reflexionsgrad mittels verfärbbarer bzw. farbneutraler Flüssigkristallschichten in Verbindung mit Polarisationsfiltern veränderbar ist sind ausserdem in den DE-OSen 29 48 514, 31 44 143 und 33 02 195 beschrieben. Durch die EP-A 0 006 811 ist schließlich eine elektrolytische Zelle bekannt, die eine transparente Elektrode sowie eine metallische Gegenelektrode aufweist, zwischen denen sich ein Elektrolyt befindet. Je nach Polarität einer an die beiden Elektroden angelegten Spannung wird auf der transparenten Elektrode eine Schicht des Metalls der metallischen Elektrode niedergeschlagen oder von dieser abgelöst. Die Zelle dient als Anzeigevorrichtung zur Darstellung von Symbolen, Zahlen und Buchstaben.There have long been dimmable rear-view mirrors for motor vehicles in which an optically active pane is arranged such that it can be tilted within the mirror and can be tilted into one of two predetermined positions by a tilting mechanism. In one position of the pane, practically all of the light falling on the mirror is reflected, so that a bright image is created. In the second position, on the other hand, only a weakened reflected image gets into the eye of the beholder, which reduces the risk of glare. Such mechanical designs are relatively complex and not user-friendly. It is also known to “electronically” dazzle mirrors. For this purpose, DE-PS 19 48 362 proposes continuously changing the absorption of an electrochromic layer, which is located between the viewer and a reflector, by applying a voltage to two electrodes that enclose the electrochromic layer. Although this level meets the legal requirements (5% ≦ R ≦ 55%), the switching times are in the order of several seconds and are therefore unreasonably long. By DE-OS 29 34 451 a dimmable rearview mirror has also become known, which uses a liquid crystal cell of the twisted nematic type (TN-LCD) between crossed polarizers. Since polarizers absorb approx. 50% of the incident light, legal requirements are difficult to meet. Typical values for the reflectance of such mirrors are 7% ≦ R ≦ 3T%. An LCD rearview mirror developed by Murakami Kameido (Japan) does not need polarizers. In the liquid crystal, dye molecules are embedded as light absorbers, which can be folded from a non-absorbent layer into an absorbent layer by applying an electric field. The efficiency of this mirror is poor. According to the manufacturer, it is 27% ≦ R ≦ 51%. Motor vehicle rear-view mirrors, the reflectance of which can be changed by means of discolourable or color-neutral liquid crystal layers in conjunction with polarization filters, are also described in DE-OSes 29 48 514, 31 44 143 and 33 02 195. Finally, EP-A 0 006 811 discloses an electrolytic cell which has a transparent electrode and a metallic counter electrode, between which an electrolyte is located. Depending on the polarity of a voltage applied to the two electrodes, a layer of the metal of the metallic electrode is deposited on the transparent electrode or detached therefrom. The cell serves as a display device for displaying symbols, numbers and letters.
Vorteile der ErfindungAdvantages of the invention
Die erfindungsgemäß vorgeschlagene Anwendung des Elektrolyseverfahrens zum Erzeugen und Ablösen einer reflektierenden Metallschicht an einer flächigen Elektrode durch Umkehrung des Stromflusses im Elektrolyten bei einem Spiegel, insbesondere bei einem Rückspiegel für Kraftfahrzeuge, erbringt demgegenüber den Vorteil, daß ein solcher Spiegel auf Umpolungen der Spannung sehr schnell reagiert, so daßsich kurze Ab- und Aufblendzeiten ergeben. Außerdem erfüllt er die gesetzlichen Vorgaben hinsichtlich Reflexionsvermögen im Hell- und Dunkelzustand, wobei die erreichbaren Kontraste höher sind als bei den bisher bekannten abblendbaren Spiegeln. Ferner benötigt der Spiegel keine Polarisatoren und kann mit handelsüblichen Materialien hergestellt werden.The proposed use of the electrolysis method for producing and detaching a reflective metal layer on a flat electrode by reversing the current flow in the electrolyte in a mirror, in particular in a rear view mirror for motor vehicles, provides the advantage that such a mirror reacts very quickly to polarity reversal of the voltage, so that there are short fade-in and fade-in times. In addition, it fulfills the legal requirements with regard to reflectivity in light and dark states, whereby the achievable contrasts are higher than with the previously known dimmable mirrors. Furthermore, the mirror does not require polarizers and can be made with commercially available materials.
Durch die in den Unteransprüchen aufgeführten Maßnahmen sind vorteilhafte Weiterbildungen und Verbesserungen des Verfahrens und eines durch Anwendung des Verfahrens hergestellten Spiegels möglich. Bevorzugt wird zur Reduzierung des Reflexions grades des Spiegels reflektierendes Metall von einer dem Beschauer zugekehrten vorderen Elektrode abgelöst und auf einer hinteren Elektrode des Spiegels niedergeschlagen. Ein anderes Verfahren, das den Schichtaufbau vereinfacht, besteht darin, daß zur Reduzierung des Reflexionsgrades reflektierendes Metall von einer hinteren Elektrode abgelöst und in körniger Form auf einer dem Beschauer zugekehrten vorderen Elektrode des Spiegels niedergeschlagen wird. Der Spiegel selbst kann zwei an eine umpolbare Spannungsquelle anschließbare flächige Elektroden haben, von denen jede auf einer den Elektrolyten einschließenden Trägerplatte angeordnet ist, wobei die dem Beschauer zugekehrte vordere Elektrode und deren Trägerplatte aus durchsichtigen Materialien bestehen, während die hintere Elektrode aus einem reflektierenden Metall gebildet ist. Bei Spiegeln, bei denen zur Reduzierung des Reflexionsgrades reflektierendes Material von der vorderen auf die hintere Elektrode verlagert wird ist es zur Erzielung eines ausreichenden Abblendeffektes zweckmäßig, daß auf die hintere Elektrode eine für Ladungsträger permeable Isolationsschicht von dunkler, vorzugsweise schwarzer Farbe, aufgebracht wird. ZeichnungThe measures listed in the subclaims allow advantageous developments and improvements of the method and of a mirror produced by using the method. To reduce the degree of reflection of the mirror, reflecting metal is preferably detached from a front electrode facing the viewer and deposited on a rear electrode of the mirror. Another method which simplifies the layer structure consists in that, in order to reduce the reflectivity, reflective metal is detached from a rear electrode and deposited in granular form on a front electrode of the mirror facing the viewer. The mirror itself can have two flat electrodes that can be connected to a polarity-reversible voltage source, each of which is arranged on a support plate enclosing the electrolyte, the front electrode facing the viewer and the support plate being made of transparent materials, while the rear electrode is made of a reflective metal is. In the case of mirrors in which reflective material is shifted from the front to the rear electrode in order to reduce the reflectance, it is expedient to achieve a sufficient dimming effect that an insulation layer of dark, preferably black color, which is permeable to charge carriers, is applied to the rear electrode. drawing
Weitere Merkmale und Einzelheiten der Erfindung ergeben sich aus der nachfolgenden Beschreibung anhand eines in der Zeichnung dargestellten Ausführungsbeispiels. Es zeigen Figur 1 die elektrolytische Zelle eines abblendbaren Spiegels in perspektivischer Darstellung, Figur 2 einen Schnitt durch die vergrößert dargestellte Zelle nach Figur 1 mit elektrischer Beschaltung.Further features and details of the invention will become apparent from the following description with reference to an embodiment shown in the drawing. 1 shows the electrolytic cell of a dimmable mirror in a perspective view, FIG. 2 shows a section through the cell shown in FIG. 1 with electrical wiring.
Be schreibung des AusführungsbeispielsBe description of the embodiment
In der Zeichnung ist mit 1 eine dem Auge 2 eines Beschauers zugekehrte obere Trägerplatte und mit 3 eine untere Trägerplatte bezeichnet. Die obere Trägerplatte 1 besteht aus einem durchsichtigen Material, vorzugsweise aus Glas. Als Werkstoff für die untere Trägerplatte 3 wird bevorzugt gleichfalls Glas verwendet. An der Innenseite der oberen Trägerplatte 1 befindet sich eine aktive Elektrode 4 aus durchsichtigem Material, vorzugsweise aus Zinn-Indium-Oxid. Eine Gegenelektrode 5 aus reflektierendem Metall z.B. Silber oder Aluminium, ist auf die Innenseite der untere Trägerplatte 3 aufgebracht. Die Trägerplattenanordnung 1, 3 ist an den Rändern ringsum hermetisch verschlossen. DerAAbstand der Platten voneinander wird über einen Rahmen 6 auf das erforderliche Maß zwischen 100 μm und 200 μm eingestellt. Das so geschaffene Volumen zwischen den beiden Trägerplatten ist mit einem Elektrolyten 7 gefüllt. Die als Gegenelektrode 5 dienende Metallschicht ist mit einer für Ladungsträger permeablen Isolierschicht 8 überzogen. Diese Schicht ist zur Verbesserung des Abblendeffekts vorzugsweise schwarz eingefärbt. Sie ist zweckmäßig als poröse Filmschicht mit einer Dicke von 0,1 bis 0,5 mm ausgebildet. Als Schichtmaterial kann beispielsweise PTFE, Polypropylen oder Polyäthylen verwendet werden. Im Ausgangszustand wird das von einer Lichtquelle 9 abgestrahlte Licht zu etwa 4 % an der Oberfläche der Trägerplatte 1 reflektiert. Dieser Wert ergibt sich aus den unterschiedlichen Brechzahlen von Luft (n = 1) und Glas (n = 1,52). Das restliche in die Zelle eindringende Licht wird durch die Isolationsschicht 8 absorbiert, sofern diese tiefschwarz eingefärbt ist. Dieser Zustand ist bei Kraftfahrzeugrückspiegeln für Nachtbetrieb vorgesehen, um den Fahrer vor Blendung durch die Scheinwerfer nachkommender Fahrzeuge zu schützen.In the drawing, 1 denotes an upper support plate facing the eye 2 of an observer and 3 denotes a lower support plate. The upper carrier plate 1 consists of a transparent material, preferably of glass. Glass is also preferably used as the material for the lower carrier plate 3. On the inside of the upper carrier plate 1 there is an active electrode 4 made of transparent material, preferably of tin-indium oxide. A counter electrode 5 made of reflective metal, for example silver or aluminum, is applied to the inside of the lower carrier plate 3. The carrier plate arrangement 1, 3 is hermetically sealed all around at the edges. The spacing of the plates from one another is adjusted to the required dimension between 100 μm and 200 μm via a frame 6. The volume created in this way between the two carrier plates is filled with an electrolyte 7. The metal layer serving as counter electrode 5 is coated with an insulating layer 8 which is permeable to charge carriers. This layer is preferably colored black to improve the anti-glare effect. It is expediently designed as a porous film layer with a thickness of 0.1 to 0.5 mm. For example, PTFE, polypropylene or polyethylene can be used as the layer material. In the initial state, approximately 4% of the light emitted by a light source 9 is reflected on the surface of the carrier plate 1. This value results from the different refractive indices of air (n = 1) and glass (n = 1.52). The remaining light penetrating into the cell is absorbed by the insulation layer 8, provided that it is colored deep black. This state is provided for motor vehicle rear-view mirrors for night operation in order to protect the driver from glare from the headlights of vehicles coming from behind.
Soll der Spiegel auf Tagbetrieb umgeschaltet werden, so wird an die Elektroden 4 , 5 mittels der Umschalter 10 die Spannung einer Batterie 11 mit solcher Polarität angelegt, daß durch den nun einsetzenden elektrolytischen Prozeß eine Metallschicht 12 (Figur 1) aus Metall der Elektrode 5 über den Elektrolyten 7 auf der ursprünglich durchsichtigen Elektrode 4 abgeschieden wird. Im Falle von Silber erfolgt die Reaktion nach dem Schema:
Figure imgf000007_0001
If the mirror is to be switched over to daytime operation, the voltage of a battery 11 is applied to the electrodes 4, 5 by means of the changeover switch 10 with such polarity that a metal layer 12 (FIG. 1) made of metal is applied to the electrode 5 by the electrolytic process that is now starting the electrolyte 7 is deposited on the originally transparent electrode 4. In the case of silver, the reaction follows the scheme:
Figure imgf000007_0001
wobei an der Gegenelektrode 5 die jeweils entgegengesetzte Reaktion abläuft. Der Prozeß ist reversibel, d.h. beim erneuten Umpolen der Spannung wird die reflektierte Metallschicht von der aktiven Elektrode h abgebaut und auf der Gegenelektrode 5 niedergeschlagen. Damit ist der Spiegel wieder für Nachtbetrieb umgeschaltet.the opposite reaction taking place at the counter electrode 5. The process is reversible, i.e. when the voltage is reversed, the reflected metal layer is broken down by the active electrode h and deposited on the counter electrode 5. The mirror is now switched back to night mode.
Bei geeigneter Zusammensetzung des Elektrolyten hat die auf der aktiven Elektrode 4 abgeschiedene Metallschicht 12 das Aussehen und die Wirkung eines metallischen Spiegels, dessen Re flexionsvermögen vom Reflexionsgrad des abgeschiedenen Metalls abhängt. Der Reflexionsgrad liegt für Silberschichten zwischen 0,90 und 0,94 und für Aluminiumschich- ten zwischen 0,80 und 0,85. Andere geeignete Reflexionsschichten sind Zinnschichten, Zinkschichten, Nickelschichten und Platinschichten, deren Ηeflexionsgrad jedoch geringer ist als derjenige von Silber- und Aluminiumschichten.With a suitable composition of the electrolyte, the metal layer 12 deposited on the active electrode 4 has the appearance and the effect of a metallic mirror, the reflectivity of which depends on the reflectance of the deposited metal. The reflectance for silver layers is between 0.90 and 0.94 and for aluminum layers between 0.80 and 0.85. Other suitable reflection layers are tin layers, zinc layers, nickel layers and platinum layers, the degree of reflection of which, however, is lower than that of silver and aluminum layers.
Ein zum Abscheiden einer hochreflektierenden Silberschicht an der als Kathode geschalteten Elektrode 4 geeigneter Elektrolyt kann beispielsweise aus einer stark verdünnten, silbernitrathaltigen Salpetersäure bestehen. Eine andere Elektrolytzusammensetzung (AgJ + UaJ in Methanol) gestattet eine Umkehrung der vorstehend beschriebenen Funktionsweise wie folgt:An electrolyte suitable for depositing a highly reflective silver layer on the electrode 4 connected as the cathode can consist, for example, of a highly dilute nitric acid containing silver nitrate. Another electrolyte composition (AgJ + UaJ in methanol) allows a reversal of the function described above as follows:
Auf der Trägerplatte 3 ist als Elektrode 5 eine Spiegelschicht aus Silber aufgebracht. Die Isolationsschicht 8 wird weggelassen. Das von der Lichtquelle 9 ausgesandte Licht durchdringt den transparenten Elektrolyten 7 und wird von der Spiegelschicht 5 in das Auge 2 des Beschauers reflektiert. Beim Anlegen einer Spannung wird bei einer Stromdichte von 20 bis 25 A/cm 2 Silber solcher Körnigkeit an der Elektrode 4 abgeschieden, daß es schwarz erscheint und somit einfallendes Licht absorbiert. Die Absorbtion solcher Silberschichten mit einer Dicke von 500 nm bis 1,5 μm ist sehr hoch. Die Abscheidung erfolgt bei Spannungen in der Größenordnung von 1 V in 50 bis 200 ms. A mirror layer made of silver is applied to the carrier plate 3 as the electrode 5. The insulation layer 8 is omitted. The light emitted by the light source 9 penetrates the transparent electrolyte 7 and is reflected by the mirror layer 5 into the eye 2 of the viewer. When a voltage is applied, silver is deposited on the electrode 4 at a current density of 20 to 25 A / cm 2 of such granularity that it appears black and thus absorbs incident light. The absorption of such silver layers with a thickness of 500 nm to 1.5 μm is very high. The separation takes place at voltages of the order of 1 V in 50 to 200 ms.

Claims

Ansprüche Expectations
1. Anwendung des Elektrolyseverfahrens zum Erzeugen und Ablösen einer reflektierenden Metallschicht (12) an einer flächigen Elektrode (4 ) durch Umkehrung des Stromflusses im Elektrolyten (7) bei einem Spiegel, insbesondere einem Rückspiegel für Kraftfahrzeuge, zum reversiblen Verändern des Reflexionsgrades.1. Application of the electrolysis method for producing and detaching a reflective metal layer (12) on a flat electrode (4) by reversing the current flow in the electrolyte (7) in a mirror, in particular a rear-view mirror for motor vehicles, for reversibly changing the reflectance.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zur Reduzierung des Reflexionsgrades des Spiegels reflektierendes Metall von einer dem Beschauer zugekehrten vorderen Elektrode ( 4 ) abgelöst und auf einer hinteren Elektrode (5) des Spiegels niedergeschlagen wird.2. The method according to claim 1, characterized in that to reduce the reflectance of the mirror reflecting metal from a facing the viewer front electrode (4) and is deposited on a rear electrode (5) of the mirror.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß zur Reduzierung des Reflexionsgrades des Spiegels reflektierendes Metall von einer hinteren Elektrode (5) abgelöst und in körniger Form auf einer dem Beschauer (2) zugekehrten vorderen Elektrode (4) des Spiegels niedergeschlagen wird.3. The method according to claim 1, characterized in that to reduce the reflectance of the mirror reflecting metal from a rear electrode (5) and is deposited in granular form on a viewer (2) facing the front electrode (4) of the mirror.
h . Sp iegel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß er zwei an eine umpolbare Spannungsquelle (11) anschließbare, flächige Elektroden (4, 5) hat, von denen jede auf einer den Elektrolyten (7) einschließenden Trägerplatte (1 bzw. 3) angeordnet ist, und daß die dem Beschauer (2) zugekehrte vordere Elektrode ( 4 ) und deren Trägerplatte (1) aus durchsichtigen Materialien bestehen,während die hintere Elektrode aus einem reflektierenden Metall gebildet ist.H . Mirror according to one of Claims 1 to 3, characterized in that it has two flat electrodes (4, 5) which can be connected to a polarity-reversible voltage source (11), each of which is mounted on a carrier plate (1 or 1) enclosing the electrolyte (7). 3) is arranged, and that the viewer (2) facing front electrode (4) and their Carrier plate (1) consist of transparent materials, while the rear electrode is made of a reflective metal.
5. Spiegel nach Anspruch 4, dadurch gekennzeichnet, daß auf die hintere Elektrode (5) eine für Ladungsträger permeable Isolationsschicht (8) von dunkler, vorzugsweise schwarzer Farbe, aufgebracht ist.5. Mirror according to claim 4, characterized in that on the rear electrode (5) a charge carrier permeable insulation layer (8) of dark, preferably black, is applied.
6. Spiegel nach Anspruch 5, dadurch gekennzeichnet, daß die permeable Isolationsschicht als poröse Filmschicht mit einer Dicke von 0,1 bis 0,5 mm ausgebildet ist.6. Mirror according to claim 5, characterized in that the permeable insulation layer is designed as a porous film layer with a thickness of 0.1 to 0.5 mm.
7. Spiegel nach Anspruch 6, dadurch gekennzeichnet, daß die poröse Filmschicht (8) aus PTFE, Polypropylen oder Polyäthylen besteht.7. Mirror according to claim 6, characterized in that the porous film layer (8) consists of PTFE, polypropylene or polyethylene.
8. Spiegel nach einem der Ansprüche 4 bis 7 , dadurch gekennzeichnet, daß die dem Beschauer (2) zugekehrte Elektrode ( 4 ) aus durchsichtigem Zinn-Indium-Oxid (ITO) besteht, und daß als Trägerplatte (1) für diese Elektrode eine Glasplatte dient. 8. Mirror according to one of claims 4 to 7, characterized in that the viewer (2) facing electrode (4) consists of transparent tin indium oxide (ITO), and that as a carrier plate (1) for this electrode, a glass plate serves.
PCT/DE1986/000104 1985-04-18 1986-03-14 Application of the electrolytic process to change the degree of reflection of mirrors WO1986006179A1 (en)

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DEP3513988.9 1985-04-18
DE19853513988 DE3513988A1 (en) 1985-04-18 1985-04-18 APPLICATION OF THE ELECTROLYSIS METHOD FOR CHANGING THE REFLECTION LEVEL OF MIRRORS

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