U.S. patent number 3,736,043 [Application Number 05/128,833] was granted by the patent office on 1973-05-29 for electrochemical molecular display and writing.
This patent grant is currently assigned to International Business Machines Corporation. Invention is credited to Carlos J. Sambucetti.
United States Patent |
3,736,043 |
Sambucetti |
May 29, 1973 |
ELECTROCHEMICAL MOLECULAR DISPLAY AND WRITING
Abstract
An electrochemical, electrically-controlled, reversible,
segmented, display method and apparatus presents character patterns
which can be erased. The apparatus includes a substrate carrying
highly reflective display electrode strips which can be
electrically addressed selectively to present characters.
Characters are displayed by producing a cloud of iodine molecules
obscuring certain electrode segments or strips composed of a noble
metal or the like normally visible through a transparent cover in
the absence of an iodine cloud. An electrolyte capable of
undergoing an electrochemical reduction-oxidation reaction yields a
molecular, highly non-reflective film on the display electrode
strips to selectively obscure the selected display strips from view
to present different characters to the viewer. Satisfactory
electrolytes include organic polar iodide compounds including
ammonium, arsonium, and phosphonium iodides. Preferably, the
electrolyte includes pentavalent nitrogen iodides with a radical
selected from the choline group such as acetylcholine,
propionylcholine and butyrylcholine iodides. The iodine molecules
provided in the film tend to remain near the electrode for a
substantial period of time to provide "short-term" memory. If
gelatine or other water soluble substances are added to the
electrolyte, which substances are inert, transparent, and which
retard migration of ions, then the duration of the memory provided
by the system is extended according to the concentration of such
substances. Alternatively, iodine lines can be used to form
characters where the gold background is present everywhere and dark
lines are written upon the display electrodes which normally are
not distinguishable from the background optically. In still another
alternative, the form of this invention electrolyte carried in a
paper can be used to provide electrochemical writing upon the
paper.
Inventors: |
Sambucetti; Carlos J. (Mohegan
Lake, NY) |
Assignee: |
International Business Machines
Corporation (Armonk, NY)
|
Family
ID: |
22437205 |
Appl.
No.: |
05/128,833 |
Filed: |
March 29, 1971 |
Current U.S.
Class: |
359/228; 361/434;
345/49; 345/105; 40/448; 430/19 |
Current CPC
Class: |
C09K
9/02 (20130101); G02F 1/1506 (20130101); B41M
5/20 (20130101) |
Current International
Class: |
B41M
5/20 (20060101); G02F 1/01 (20060101); C09K
9/02 (20060101); G02F 1/15 (20060101); G02f
001/28 () |
Field of
Search: |
;350/160,267,312
;317/231 ;340/336 ;40/28C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wibert; Ronald L.
Assistant Examiner: Godwin; Paul K.
Claims
I claim:
1. An electrochemical data presentation apparatus including:
a. a pair of electrodes,
b. one of said electrodes comprising a data presentation electrode
including a noble metal selected from gold, platinum, iridium and
rhodium,
c. 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 light transmitting characteristics of said
medium as a function of the proportion of said compound comprising
said reaction product,
d. a container holding said electrodes and said medium containing
said electrolytic compound,
e. said reaction product when produced being present in said medium
adjacent to said data presentation electrode, and
f. said reaction product being suspended in said fluid medium.
2. An electrochemical data presentation apparatus including:
a. a pair of electrodes,
b. one of said electrodes comprising a data presentation electrode
including a noble metal selected from gold, platinum, iridium and
rhodium,
c. 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,
d. a container holding said electrodes and said medium containing
said electrolytic compound, and
e. said electrolytic compound comprising an organic polar iodide
compound selected from the group including ammonium, arsonium, and
phosphonium compounds.
3. An electrochemical data presentation apparatus including:
a. a pair of electrodes,
b. one of said electrodes comprising a data presentation electrode
including a noble metal selected from gold, platinum, iridium and
rhodium,
c. 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,
d. a container holding said electrodes and said medium containing
said electrolytic compound, and
e. said electrolytic compound comprising a pentavalent nitrogen
compound of the general formula ##SPC10##
where R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are selected from
hydrogen, alkyl, and aromatic groups including both simple and
substituted forms.
4. Apparatus in accordance with claim 3 wherein said choline groups
are selected from acetylcholine, propionylcholine and
butyrylcholine iodides.
5. Apparatus in accordance with claim 4 in which the concentration
of said electrolytic compound varies from 0.5 to 20 percent by
weight in solvent.
6. Apparatus in accordance with claim 4 wherein the concentration
of said electrolytic compound is approximately 2.5 percent by
weight in solvent.
7. An electrochemical data presentation apparatus including:
a. a pair of electrodes,
b. one of said electrodes comprising a data presentation electrode
including a noble metal selected from gold, platinum, iridium an
rhodium,
c. 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,
d. a container holding said electrodes and said medium containing
said electrolytic compound, and
e. said medium comprising an electrolytic solution of said
electrolytic compound and a soluble, non-reactive material added to
said electrolytic solution for retarding motion of substances in
said electrolytic solution.
8. Apparatus in accordance with claim 7 wherein said non-reactive
material is gelatine added in sufficient concentration to increase
viscosity of said solution.
9. An electrochemical data presentation apparatus including:
a. a pair of electrodes,
b. one of said electrodes comprising a data presentation electrode
including a noble metal selected from gold, platinum, iridium and
rhodium,
c. 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,
d. a container holding said electrodes and said medium containing
said electrolytic compound, and
e. said one electrode including a basic layer of copper supported
upon a substrate, an intermediate layer of palladium and an outer
layer of gold.
10. Apparatus in accordance with claim 9 with said palladium layer
electrodeposited upon the copper base and said gold layer plated
upon said palladium.
11. Apparatus in accordance with claim 2 wherein the other of said
electrodes comprises a reference electrode composed of silver and
silver iodide.
12. An electrochemical radiation reflection controlling apparatus
including:
a. a pair of electrodes,
b. at least one of said electrodes having a light reflecting
surface, said surface being composed of an inactive substance,
c. electrical terminals connected to said electrodes,
d. an electrolytic fluid comprising means for providing 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,
e. and a container holding said electrodes and said
electrolyte.
13. An electrochemical reflection controlling device including:
a. a pair of electrodes at least one of which is composed of noble
metal material,
b. an electrolyte containing an organic compound of pentavalent
nitrogen with an iodide ion combined in the compound,
c. at least one of said electrodes having a radiation reflecting
surface,
d. electrical terminals attached to said electrodes,
e. and a container including said electrodes and said
electrolyte.
14. 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,
b. an electrolyte containing an organic compound of pentavalent
nitrogen with a negative iodide ion included in the compound and a
choline group comprising a radical of a positive ion including the
nitrogen,
c. a container including said electrodes and said electrolyte.
15. Apparatus in accordance with claim 14 wherein said compound is
selected from a group including acetylcholine iodide and
propionylcholine iodide.
16. An electrochemical display apparatus including:
a. a pair of electrodes,
b. one of said electrodes including a noble metal with high
reflection characteristics selected from gold, platinum, iridium
and rhodium,
c. and an electrolyte providing a reversible reduction-oxidation
reaction product in said electrolyte adjacent to said electrode at
the end of said reaction for absorbing radiation, said reaction
product composed of free molecules of an anion and providing a
change in the reflection from said one electrode,
d. and a container holding said electrodes and said
electrolyte.
17. An electrochemical data presentation method including:
a. employing a pair of electrodes,
b. using one of said electrodes including a noble metal selected
from gold, platinum, iridium and rhodium as a data presentation
electrode,
c. and employing a medium for presentation of indicia, said medium
containing an electrolytic compound yielding an electrochemical
reversible reduction-oxidation reaction product suspended in said
medium adjacent to said one electrode composed of free molecules of
an anion for absorbing radiation and thereby changing the
transmission characteristics of said medium to present data formed
by passing direct current between said electrodes with a positive
potential upon said one electrode.
18. 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.
19. A method in accordance with claim 17 including employing as
said electrolyte a pentavalent nitrogen compound of the general
formula ##SPC11##
where R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are selected from
hydrogen, alkyl, and aromatic groups which can be simple and
substituted.
20. An electrochemical radiation reflection controlling apparatus
including:
a. a pair of electrodes,
b. at least one of said electrodes comprising a display electrode
having a surface adapted for reflection of radiation, said surface
being composed of gold,
c. 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 plated upon said palladium, the other
of said electrodes comprising a reference electrode composed of
silver and silver iodide,
d. an electrolyte, said electrolyte being a pentavalent nitrogen
compound of the genera formula ##SPC12##
where R.sub.1, R.sub.2, R.sub.3 and R.sub.4 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,
e. electrical terminals connected to said electrodes,
f. 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,
g. a soluble, non-reactive material including gelatin being added
to said electrolytic solution for retarding motion of substances in
the electrolyte to increase viscosity,
h. and a container holding said electrodes and said
electrolyte.
21. Apparatus in accordance with claim 1 wherein said electrolytic
compound comprises an iodide and said reaction product comprises
free molecules of iodine.
22. Apparatus in accordance with claim 1 wherein said electrolytic
compound comprises an organic halide and said reaction product
comprises free molecules of said halide.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of electrochemical display and
writing devices providing changeable signs exhibiting patterns
under electrical control.
In addition, this invention relates to chemical, electrical and
wave energy electrolytic apparatus and a method for providing an
electrochemical display and for electrochemical writing.
In addition, this invention relates to electrically operated
registers including an electrochemical display apparatus combined
with data storage.
2. Description of the Prior Art
Electrochemical cells have been employed for the purpose of
providing electrochemical displays by means of electrochemical
plating or by use of reactive electrodes which are tarnished by a
reaction between the electrode and the electrolyte. However, the
prior art available has not suggested use in displays of inactive
or noble metal electrodes without reaction of the electrodes or
plating of the electrodes. A problem with both of these techniques
of display regardless of the anions and cations employed is that
while the chemical reactions may be reversible, they are only
partially reversible from the point of view of their implementation
in displays. The problem which occurs is that the electrodes become
coated with oxides of materials upon their surfaces which gradually
blacken the display surfaces even if the underlying electrode is a
noble metal an other less reflective or different colored metals
are electroplated thereon.
SUMMARY OF THE INVENTION
Accordingly, 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.
In accordance with this invention, an electrochemical display
apparatus is provided 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. A corresponding method is provided. Preferably the
electrolyte comprises an organic polar iodide compound selected
from the group including ammonium, arsonium, and phosphonium
compounds. Preferably, the electrolyte is a pentavalent nitrogen
compound of the general formula ##SPC1##
where R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from
hydrogen, alkyl, and aromatic groups which can be simple and
substituted. The choline groups can be selected from acetylcholine,
propionylcholine and butyryl-choline 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.
Preferably, 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. One
electrode includes a basic layer of copper supported upon a
substrate, an intermediate layer of palladium and an outer layer of
gold. The palladium is electrodeposited upon the copper base and
gold is plated upon the palladium. The other of the electrodes
comprises a reference electrode composed of silver and silver
iodide.
In another aspect, 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
reduction-oxidation 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.
BRIEF DESCRIPTION OF THE DRAWING
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.
DETAILED DESCRIPTION OF THE DRAWINGS
Referring to FIGS. 1-3, 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 aqueous
or water-alcohol solution of organic iodide compound, preferably
one of the pentavalent nitrogen compounds in which iodine is
attached to the nitrogen as follows: ##SPC2##
Preferably, 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. ##SPC3##
The display electrodes 11-17 are connected by wires 31-37 to
switches 41-47 and through them to the anode of battery 22, whose
cathode is connected via lines 38 to the reference electrodes 23,
24 and 25 in the display device 10. The reference electrodes 23, 24
and 25 composed of silver and silver iodide are spaced about the
device 10 so that the display electrodes 11-17 are substantially
equidistant from a reference electrode so that the time required
for each electrode to change "color" is substantially the same as
every other electrode. Thus, the display will be presented over all
of the display electrode segments 11-17 substantially at once
rather than appearing in a fragmented fashion over a period of
time, here and there.
When current is passed from battery 22 through display electrode
11-17 (which becomes an anode) through the electrolyte, and the
reference electrodes 23, 24 and 25, a film of molecular iodine
(I.sub.2) is formed adjacent to that display electrode (11-17) and
remains in juxtaposition therewith. However, the film is subject to
diffusion with time which varies inversely as a function of the
concentration of the electrolyte and as a function of the viscosity
of the solution. Display electrodes 11-17 should have rugged
surfaces to insure better adherence of the film formed on them.
When switches 41 to 47 are reversed, display electrodes 11-17
become cathodes and the current is reversed to dissipate the iodide
cloud. All of the cover 19 except for the area over anodes 11-17
has a mask 26 thereover to highlight the characters through frame
27.
Because of the wetting nature of the pentavalent nitrogen organic
solution, 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 width is not spread and dispersal is
slower.
Simultaneously, with formation of the film at the display electrode
11-17, serving as an anode, 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 1.5 volts. As a consequence of the
electrochemical reactions, 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.
If, under the same voltage, 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. In fact, the noble metal does not participate in the reaction
and acts only as an interface for electron exchange between the
external circuit and 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
corresponding 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:
(Transparent) 2I.sup.-+2e.revreaction.I.sub.2 (Film)
Essentially, the electrolyte system consists of a certain amount of
##SPC4##
dissolved in water. R.sub.1, R.sub.2, R.sub.3 and R.sub.4 can be
either alifatic (methyl, ethyl, . . . , etc.) or aromatic groups
(phenyl, benzoyl groups) either the same or different. For example,
both trimethyl-phenyl ammonium iodide and dimethylethyl-benzoyl
ammonium iodide work reasonably well. However, if the resulting
compound is not readily soluble in water, it is necessary to use
water-alcohol or other solvent mixtures.
Best results are obtained when one of the radicals belongs to the
choline group. For example, acetylcholine and propionylcholine
iodides are excellent, especially when the aqueous concentration is
maintained between two to 6 grams percent. ##SPC5##
Acetylcholine Iodide Legend
To achieve improved memory, the solution of electrolyte includes 3
percent by weight of gelatin, which increases persistency of the
film by enhancing its adherence to the electrode surface.
I. variations in pentavalent nitrogen compound formulation
Starting with the basic formula ##SPC6##
The simplest compound of pentavalent nitrogen is one of which all R
groups are hydrogen, which is ammonium iodide ##SPC7##
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 film does not adhere to the electrode and
there is considerable bleeding of the film around the display
segment 11-17.
Similar behavior is observed with trimethyl and triethylammonium
iodide. Use of 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.
A second observation is that acetylcholine iodide and
propionylcholine iodide are both very satisfactory. As the
molecular weight of the compound increases, for example, with
butyrylcholine iodide, the solubility in water of the compound
decreases and besides the film produced in writing erases less
readily.
Acetylcholine iodide and propionylcholine iodide electrolytes are
operative within a temperature range from 0.degree.C to 85.degree.C
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 10.degree.C at which the electrolyte
tends to gell and 50.degree.C at which the electrolyte evaporates
and memory deteriorates.
With increasing molecular weight and complexity, for example, with
benzoylcholine iodide, the compound is insoluble in water and is
unsatisfactory as an electrolyte in that case. However,
water-alcohol mixtures of benzoylcholine iodide are soluble and
good writing-erasing effect is obtainable.
The pentavalent nitrogen choline compounds are satisfactory in
mixtures in which the solvent is a solvent such as methanol,
ethanol, acetone, D.M.S.O. Two problems arise in these mixtures:
(a) the solvent tends to evaporate, and (b) the film produced in
writing dissolves more rapidly to provide a shorter memory.
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.
Ii. 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 writing-erasing 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.
Iii. optimum cell chemistry
Acetylcholine iodide or propionylcholine iodide give excellent
results. A concentration of 2.5 grams of acetylcholine iodide in
100 grs. of water gives fast speed with a memory duration of less
than 1 minute. To increase memory or permanency of the presence in
the display of the film, gelatin is added to the solution. The
amount of 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.
One can evaluate the active mass of electrolyte involved in the
writing of a given character as well as the percentage loss of
iodine film per character as a function of the time that a
character is "on" before electrical erasing occurs.
To distinctly write a character of 0.08 square inch surface area
(made of 7 mm .times. 1 mm segments) requires depositing 8 .times.
10.sup..sup.-6 grams of iodine. The electrolyte solution around
each character has available 0.7 grams of iodine, and allows
writing (0.7/8) 10.sup.6 characters. Studies indicate that only 50
percent of the iodine film migrates to the solution as free iodine.
The rest reconverts back to iodide available for further writing.
Therefore, the number of characters that can be written, assuming
that each one is left alone to dissipate totally in the electrolyte
(process that takes more than 3 minutes) is twice as much or (2
.times. 0.7/8) 10.sup.6 characters.
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 80 column card in about 20
seconds, thus producing roughly 10.sup.5 character/8 hour day.
Assuming for such applications that 10 percent of the film will be
lose per character on an average (loss will be maximum for the
first character of an 80 column card, and minimum for the 80th
character), the approximate life of the electrolyte (without the
re-generation) will be: ##SPC8##
Iv. improvements in Acetylcholine Iodide Cells
Changes in cell structure: The cell reference electrode can be a
gold bar placed alongside or around the gold-plated character. The
problems associated with this are that when writing iodine on a
character at voltages over 1.5 (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 on
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: ##SPC9##
When writing on the gold character strips (character (+) and
reference (-)) iodide ions enter the solution from the AgI
reference while other iodide ions leave it to form the film of
iodine on the gold. During erasing, the film of iodine over the
gold is converted back to iodide, and the reference silver and
iodide regenerate the AgI layer. Both end products of the reference
electrode reactions are insoluble (silver and silver iodide) except
for the iodide ions which are produced or captured by the
reference.
a. The silver, silver iodide electrode allows writing iodine on
gold characters as faster speeds (voltages over 2 volts) without
gas evolution, because the dissociation for AgI occurs
preferentially to the electrolysis of water.
b. Erasing also occurs with no gas evolution at the reference. If
the erasure is voltage-controlled at the gold character in order to
stop current flow where the gold surface is iodine free, the
problem of gas generation is solved altogether.
c. Short circuiting the reference overnight with a gold bar placed
in a cell containing substantial amounts of free iodine, completely
purges the cell of dispersed iodine, while forming more AgI at the
reference.
The reversible writing process in these cells consists in the
electrical generation of sufficient iodine to form a character. In
the erasing process the film is electrically reduced back to
iodide. If, during 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.
However, 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. This tends
to remove iodide ions from the electrolyte producing a gradual
exhaustion which limits the electrolyte life. The exhaustion
process will depend on the initial concentration of iodide, on the
number of characters written per unit time and on the interval
lapsed between writing and erasing.
If the operation of the display is such that the characters are
electrically erased a few seconds after being displayed, then the
amount of iodine lost by migration is minimum and the cell life is
considerably longer.
Employing the current required to erase the film from the display
as a source of memory, a computer or other data processing device
can read the display by providing a potential for erasing and
measuring the resultant current for the various display electrodes
11-17.
In electrochemical displays it is desirable that some means be
provided for altering the appearance of the display in response to
an electrical signal. This can be done by changing the reflection
of the light or the color or both. For example, it is desirable to
provide a surface that is visible to the observer. It is also
desirable to provide a structure which will permit changing the
appearance of the surface being viewed from light reflecting to
light absorbing and to provide that change at such a speed that the
process is compatible with the speed of data processing or data
transmission devices. 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 at low applied
voltages which are compatible with semiconductor or transistor
circuits.
In addition, 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.
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.
If 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.
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