U.S. patent number 3,831,179 [Application Number 05/316,001] was granted by the patent office on 1974-08-20 for electrographic tape recording medium.
This patent grant is currently assigned to Robert Bosch GmbH. Invention is credited to Klaus Brill, Wolfgang Grothe.
United States Patent |
3,831,179 |
Brill , et al. |
August 20, 1974 |
ELECTROGRAPHIC TAPE RECORDING MEDIUM
Abstract
A layer of a metallic oxide having a heat of formation less than
that of aluminum oxide is provided between the paper or synthetic
flexible carrier and an aluminum film having a square resistance of
about 2.5 ohms. Electric current flows between a stylus and the
aluminum layer, but the effect of the current is merely to initiate
an aluminothermic reaction between the aluminum and the oxide
which, however, is sharply limited to the path of the stylus over
the medium as the stylus or the medium is moved, leaving a clearly
visible trace.
Inventors: |
Brill; Klaus (Korntal,
DT), Grothe; Wolfgang (Stuttgart, DT) |
Assignee: |
Robert Bosch GmbH (Stuttgart,
DT)
|
Family
ID: |
5834595 |
Appl.
No.: |
05/316,001 |
Filed: |
December 18, 1972 |
Foreign Application Priority Data
Current U.S.
Class: |
347/221; 400/241;
346/135.1 |
Current CPC
Class: |
B41M
5/245 (20130101) |
Current International
Class: |
B41M
5/24 (20060101); B41m 005/18 () |
Field of
Search: |
;346/135,76,74
;117/222,215,217 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Wilkinson; Richard B.
Assistant Examiner: Miska; Vit W.
Attorney, Agent or Firm: Flynn & Frishauf
Claims
We claim:
1. A recording medium for graphic recording devices comprising:
a flexible tape of insulating material serving as a carrier
layer;
a covering layer consisting essentially of aluminum;
an intermediate layer between said carrier layer and said covering
layer composed of one or more oxides of at least one metal selected
from the group consisting of manganese, chromium, iron, cobalt,
nickel and tin, said oxide or oxides having a heat of combination
less negative than aluminum oxide,
said intermediate and covering layers being mechanically supported
on said tape.
2. A recording medium as defined in claim 1 in which said
intermediate layer is composed essentially of one or more oxides of
manganese.
3. A recording medium as defined in claim 1 in which said
intermediate layer has a thickness between 0.005 and 1 micron and
said covering layer has a thickness between 0.01 and 0.5
micron.
4. A recording medium as defined in claim 3 in which said
intermediate layer has a thickness between 0.01 and 0.5 micron and
said covering layer has a thickness of between 0.02 and 0.1 micron.
Description
This invention relates to a recording medium for graphic recording
devices using a tape of insulating material as a carrier and having
a covering layer composed essentially of aluminum.
The recording process utilizing known graphic recording media of
this type uses a writing stylus through which an electric current
flows into or out of the aluminum. The current flow under the point
of the stylus melts the metal layer by means of the Joule heat
produced. The layer coalesces there, the electrical contact is
broken, and an arc is formed. The arc burns the layer out up to a
certain spot size and then extinguishes. This process is repetitive
if the paper or the stylus is advanced and a new contact is
produced. The writing trace is thus formed by a series of discrete
burnouts.
All the energy necessary for burning out aluminum in these graphic
recording media has been provided by the electric arc. In the
entire region of the arc plasma very high temperatures are reached.
In consequence, the layer material vaporizes and is ionized in the
plasma. By convection and under the influence of the electric
field, a transfer of material takes place so that scales of
aluminum oxide are formed on the stylus. These scales lead to
interruption of the flow of current and thus also of the writing
trace. For this reason, high writing voltages and stylus
application pressures are necessary. The high mechanical and
thermal stressing of the stylus leads to indications of wear of the
stylus point as well as to so-called trails on the paper, which are
weakly visible traces that arise even though neither a flow of
current nor an arc was present. The causes of these "trails" are
still unknown.
A further disadvantage of the known graphic recording media, even
those with aluminum base, lies in the relatively high corrosion of
the metal layer. Especially when resin coated paper is used as the
carrier layer, solvent residues from the resin layer as well as
materials containing acid or alkali groups which are likely to rub
off the surface of pigment grains, come into contact with the metal
layer, where they promote the corrosion of the metal. That means
that the durability of the cover layer cannot yet be regarded or
designated as satisfactory in many cases involving known graphic
recording media.
A further disadvantage of the known graphic recording media is the
polarity dependence of the quality of the traces produced. With the
known graphic recording media, sharply bounded traces are obtained
if the stylus has negative polarity. That leads, however, to
relatively frequent gaps because in that case aluminum oxide is
readily formed on the stylus, so that a higher application pressure
is needed. For that reason, the stylus is generally connected to
the positive pole of the voltage source in spite of the fact that
the trace is not so sharply defined in that case. It is possible to
reduce the application pressure in that fashion, however, because
with positive polarity aluminum oxide no longer forms to the same
extent at the stylus point.
It is the object of the present invention to improve the quality
and the safety in operation of graphic recording media. In
particular, it is an object to avoid or mitigate the formation of
oxide layers or scale at the stylus point, so that the recording
device can be operated with low application pressure, thus largely
avoiding wear of its mechanically stressed parts. In addition, it
is desirable for the quality of the inscribed traces to be, so far
as possible, independent of polarity, so that this too is an object
of the invention. Finally, it is an object of the invention to
provide a graphic recording medium of high corrosion resistance and
thereby to provide a medium of increased durability.
SUBJECT MATTER OF THE PRESENT INVENTION
Briefly, instead of supplying all the energy for the formation of
the trace through the arc that is formed, a large proportion of the
necessary energy is stored in the writing layer of the medium
itself, in the form of latent chemical energy. This is accomplished
by providing a layer of an oxide having a lower heat of formation
less negative than that of aluminum oxide in between the carrier
layer and the aluminum covering. Heat of formation is generally
expressed with reference to 1 gram-atom of oxygen, so that the
value for Al.sub.2 O.sub.3 is minus 133 kilocalories per gram-atom
of oxygen.
The graphic recording process involved in the application of the
recording medium of the invention may be described as follows. The
electric current flowing between the stylus point and the aluminum
covering layer, by warming the layer and producing an arc sets off
an exothermic reaction which delivers most of the necessary energy
for producing the trace. This exothermic reaction is a so-called
aluminothermic reaction. When manganese oxide, Mn.sub.3 O.sub.4, is
used for the intermediate layer, the reaction may be written as
follows:
8 Al + 3 Mn.sub.3 O.sub.4 .fwdarw. 4 Al.sub.2 O.sub.3 + 9 Mn +
.DELTA.H = 607 kcal.
THe amount of energy liberated depends upon the total amount of
conversion as well as upon the stage or state of oxidation in which
the metal in question (in this case manganese) is provided.
By inspection of the energy balance, it is evident that the energy
liberated by the reaction with manganese oxide, Mn.sub.3 O.sub.4,
is by itself sufficient to vaporize an aluminum coating having a
square resistance of 2.5 ohms, which corresponds to a mass
distribution of 10 .mu.g/cm.sup.2. The fact that the place at which
the formation of the trace takes place has been shifted from the
arc plasma into the layer itself is doubtless responsible for the
good quality of the traces obtained with the graphic recording
medium of this invention. In this fashion, a local limitation or
confinement of the reaction is reached that leads to very sharp
traces. It has moreover been found that no polarity effect or
influence is to be distinguished in the use of the graphic
recording medium of the invention. The writing sensitivity of the
layer is thus practically independent of the polarity of the
stylus.
It furthermore appears that the intermediate metal oxide layer has
the important effect of blocking the diffusion of the corrosive
groups originating in the carrier layer, which tend to corrode the
aluminum covering layer. In this manner the useful life of the
aluminum layer of the graphic recording medium of the invention is
substantially increased. It was determined by comparative corrosion
tests that in the case of the aluminum layer of the new graphic
recording medium, no attack of the aluminum layer was yet
recognizable when the aluminum layers of recording media of
previously used types already showed clearly visible corrosion
effects.
In principle, all oxides having a heat of formation number with
reference to 1 gram-atom of oxygen, that is smaller than that of
aluminum oxide can be used for the middle layer of the recording
medium. For the present purposes, however, certain aspects must be
taken into account which come into play in connection with the
production of the layers or in connection with the process of trace
formation. In the first place, it is important that the oxide layer
should be capable of being applied to the carrier layer in the
simplest possible way. Next, the oxide layer serving as an
intermediate layer should have no electric conductivity, for
otherwise, because of the fact that the overall conductivity is
composed of the partial conductivities of the adjoining materials
and that the area resistance of the layer should amount to 2.5
ohms, the aluminum cover layer would have to be so thin as to
become transparent. That is undesirable, since in that case the
traces would not be clearly recognizable, especially in transmitted
light.
Taking account, therefore, of these various aspects, it is
particularly advantageous for the oxide layer to consist of one or
more oxides of at least one of the following metals: manganese,
chromium, iron, cobalt, nickel, tin.
The oxide layers can be applied to the carrier by known methods, as
for example, direct vapor deposition, reactive vapor deposition,
vapor deposition of the metal and subsequent oxidation, chemical
vapor deposition or chemical precipitation from solution.
The individual layers of the graphic recording medium should
appropriately have the following thicknesses: The carrier layer
should have a thickness from 5 to 500 microns (.mu.m), preferably
10 to 100 .mu.m; the metal oxide layer should have a thickness from
0.005 to 1 .mu.m, preferably 0.01 to 0.5 .mu.m, and the aluminum
layer a thickness from 0.01 to 0.5 .mu.m, preferably 0.02 to 0.1
.mu.m.
Illustrative examples of the invention are further described with
reference to the accompanying drawing, wherein:
FIG. 1 is a cross-section of a graphic recording medium using an
uncoated layer of synthetic material as a carrier, and
FIG. 2 is a cross-section of a graphic recording medium using a
resin coated paper carrier layer.
In FIG. 1 the carrier layer 11 consists of a synthetic material
film having a thickness of 50 .mu.m. On this carrier a manganese
oxide layer 12 is applied. This is accomplished by so-called
reactive vapor deposition, i.e., the carrier tape 11 is exposed to
manganese vapor in the presence of steam in a vapor deposition
apparatus, so that manganese oxide, essentially Mn.sub.3 O.sub.4 is
formed. The thickness of this manganese oxide layer amounts to
about 0.1 .mu.m. In a further operation, an aluminum layer of about
0.07 .mu.m is laid down on this manganese oxide layer in a second
vapor deposition apparatus.
In FIG. 2 the carrier tape consists of a paper sheet 21 provided
with a resin coating 22. Both together have a thickness of about 80
.mu.m. On the resin layer 22, a manganese oxide layer 23 of about
0.08 .mu.m thickness is vapor deposited in the same way as
described above and thereon also likewise an aluminum layer 24 of
the same thickness.
It is also possible to carry out vapor deposition of the oxide
layer and of the aluminum layer one after the other in the same
vapor deposition equipment, if a suitably constructed vapor
deposition apparatus is available.
A comparison of the graphic recording media of the present
invention illustrated in FIGS. 1 and 2 and described just above,
with known recording media of the kind previously mentioned,
provides the following comparative values:
For a particular standardized trace width and trace quality, a
writing voltage from 30 to 35 volts was necessary in the case of
the previously known recording media, whereas the same trace width
and the same trace quality was already obtained with a writing
voltage of 20 volts in the case of the recording medium of the
present invention. With a stylus application pressure of 35 mp
(milliponds) excellent traces could still be produced on the
graphic recording medium of the invention, and actually also
independent of whether the stylus was polarized negatively or
positively with respect to the medium. For the previously known
graphic recording media, on the other hand, with the same
application pressure and negative stylus polarity, no more writing
trace was visible and with positive stylus polarity, only an
erratic writing trace with gaps could be obtained.
The improved corrosion resistance and the resulting layer
durability of the graphic recording medium of the invention
compared to the previously known recording media has already been
mentioned above.
Although the invention has been described with reference to
particular illustrative embodiments, it is to be understood that
modifications and variations may be made within the inventive
concept without departing from the spirit of the invention.
* * * * *