U.S. patent number 3,900,634 [Application Number 05/378,402] was granted by the patent office on 1975-08-19 for glazing panel with conductive strips.
This patent grant is currently assigned to Glaverbel-Mecaniver S.A.. Invention is credited to Pierre Demoulin, Emile Plumat.
United States Patent |
3,900,634 |
Plumat , et al. |
August 19, 1975 |
Glazing panel with conductive strips
Abstract
An electrically heatable transparent glazing panel composed of a
transparent glass substrate is provided with at least one
electrically conductive coating strip by applying onto the
substrate a coating composition composed of a suspension or paste
incorporating metal particles and intermixed glass particles, at
least some of which are of a glass having a softening point lower
than that of the glass of the substrate, substantially all of which
particles are less than 5 microns in size, and subesquently firing
the applied composition. In the composition, the proportion of
metal particles is sufficient to render the resulting coating
electrically conductive.
Inventors: |
Plumat; Emile (Gilly,
BE), Demoulin; Pierre (Fleurus, BE) |
Assignee: |
Glaverbel-Mecaniver S.A.
(Watermael-Boitsfort, BE)
|
Family
ID: |
19727123 |
Appl.
No.: |
05/378,402 |
Filed: |
July 12, 1973 |
Foreign Application Priority Data
Current U.S.
Class: |
428/208; 219/203;
219/522; 252/512; 338/308; 427/108; 427/98.4; 427/97.4; 252/514;
428/210 |
Current CPC
Class: |
H05B
3/84 (20130101); B41M 1/34 (20130101); B41M
1/12 (20130101); H05B 2203/017 (20130101); Y10T
428/24909 (20150115); Y10T 428/24926 (20150115) |
Current International
Class: |
B41M
1/12 (20060101); B41M 1/26 (20060101); B41M
1/34 (20060101); H05B 3/84 (20060101); C23c
017/00 (); H05b 003/12 () |
Field of
Search: |
;117/211,227,212
;252/512-515 ;338/308,309 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Esposito; Michael F.
Attorney, Agent or Firm: Spencer & Kaye
Claims
We claim:
1. In a method of manufacturing an electrically heatable
transparent glazing panel by providing a transparent glass
substrate with at least one electrically conductive coating strip
in which heat can be generated by the Joule effect, the improvement
comprising: applying onto said substrate, to form at least one such
strip, a coating composition composed of a suspension or paste
incorporating electrically conductive metal particles substantially
all of which are below 5 microns in size, intermixed with glass
particles, the glass particles being composed of intermixed
particles of lead borosilicate glasses of different softening
points, at least the lower one of which softening points is lower
than that of the glass composing said substrate, and substantially
all of which glass particles are below 5 microns in size; and
subsequently firing such applied composition to cause at least that
one of such glasses which has such lower softening point to serve
as a binder for the metal particles; and wherein the metal
particles are present in the composition in sufficient proportion
in relation to the glass particles to render the coating strip
electrically conductive.
2. A method as defined in claim 1 wherein the glass particles have
substantially the same average grain size as the metal
particles.
3. A method as defined in claim 1 wherein at least 10%, by weight,
of the glass having the higher softening point is constituted by
oxides of aluminum and titanium, or of aluminum, titanium and
zirconium.
4. A method as defined in claim 1 wherein the glass having the
higher softening point comprises oxides of aluminum, titanium,
zirconium and cadmium in an aggregate proportion of at least 10%,
by weight, of such glass.
5. A method as defined in claim 1 wherein said metal particles
constitute at least 40% of the total aggregate weight of metal
particles and glass particles.
6. In a transparent glazing panel composed of a glass substrate
carrying at least one attached electrically conductive coating
strip in which heat can be generated by the Joule effect, the
improvement wherein said strip comprises electrically conductive
metal particles together with intermixed lead borosilicate glasses
of at least two different softening points, at least the lower
softening point glass serving as a binder for said metal particles,
substantially all of the metal particles are below 5 microns in
size and at least the higher softening point glass is present in
the form of particles substantially all of which are below 5
microns in size.
7. A panel as defined in claim 6 wherein at least 10%, by weight,
of the glass having the higher softening point is constituted by
oxides of aluminum and titanium or of aluminum, titanium, and
zirconium.
8. A panel as defined in claim 6 wherein the glass having the
higher softening point comprises oxides of aluminum, titanium,
zirconium and cadmium in an aggregate proportion of at least 10%,
by weight, of such glass.
9. A panel as defined in claim 6 wherein said metal particles are
silver particles and comprise at least 40%, by weight, of the
aggregate weight of the silver and glass particles.
10. A panel as defined in claim 6 wherein said metal particles are
silver particles and comprise less than 60% by weight of the total
of silver particles and glass particles, and further comprising a
coating covering at least part of said strip and comprising at
least 60%, by weight, silver particles.
Description
BACKGROUND OF THE INVENTION
The invention relates to a method of manufacturing an electrically
heatable transparent glazing panel, and particularly a method
involving providing a transparent glass substrate with at least one
electrically conductive coating strip in which heat can be
generated by the Joule effect. The invention also relates to
transparent glazing panels composed of a glass substrate carrying
one or more attached electrically conductive coating strips in
which heat can be thus generated.
Electrically heatable transparent glazing panels incorporating
electrically conductive elements are extensively and increasingly
used, as, or as components of, vehicle glazings, e.g., as glazing
panels in aircraft and as rear glazing panels in road vehicles.
Such glazing panels can be connected to a source of E.M.F. so that
sufficient heat is generated by the passage of electric current
through the conductive elements to keep the panel free from mist
and ice.
The production of anti-mist glazing panels by providing a glass
substrate with adherent electrically conductive coating strips has
been the subject of considerable research in industry and various
such products are available on the market. However the formation of
electrically conductive coatings with fully satisfactory properties
involves numerous problems which so far have not been solved.
It is usually necessary for the electrically conductive coatings to
adhere very strongly to the substrate, and it may even be necessary
in some cases for the coating to be resistant to impairment or
detachment from the substrate when this is subjected to a certain
amount of flexure. In cases in which the coatings are to be exposed
on an external face of the substrate, as distinct from being
sandwiched between the substrate and a superimposed protective
sheet or layer, the coatings should have good abrasion
resistance.
Another important condition to be fulfilled in products of high
quality is a high degree of uniformity in the composition of the
coatings on a given substrate and, in mass production manufacture,
a high degree of uniformity in the composition of the coatings from
one substrate to another.
This requirement of uniformity and reproducability in mass
production manufacture has proved particularly difficult to fulfill
without resorting to complex and expensive production methods.
In fact, specialist manufacturers in this field have resorted to
production methods in which successive layers of a coating
composition are applied to build up a coating in successive stages
while monitoring the electrical resistivity of the panel and using
the measured resistivity as a control factor in the application of
the coating.
Another method which has been used involves the application of
coating composition in excess of what is required followed by a
controlled removal of deposited composition in dependence on
electrical resistivity readings. Apart from being unduly expensive,
these procedures do not ensure the required uniformity in the
properties of the coatings because the resistivity measurements are
necessarily measurements of the resistivity of the whole panel.
Clearly a constant predetermined resistivity reading is compatible
with a substantial variation in conductivity from one part of a
conductor or conductor system to another and from one complete
conductor or conductor system to another.
SUMMARY OF THE INVENTION
In view of the above considerations, it is an object of the present
invention to achieve a method by which electrically heatable
transparent glazing panels with substantially uniform electrically
conductive coating strips can be manufactured in a relatively
simple manner.
Another object of the invention is to provide such a method by
which predetermined results can easily be reproduced by repetitive
performance of the method in mass production manufacture.
A further object of the invention is to provide a method which can
easily be adapted for achieving a wide range of strip
conductivities.
Yet another object, which is fulfilled by preferred embodiments of
the invention, is to enable conductive coating strips to be formed
which have a particularly high abrasion resistance.
An important field of use of the invention is the manufacture of
electrically heatable glazing panels for use in vehicle
windows.
These and other objects are achieved, according to the present
invention, by a method of manufacturing an electrically heatable
transparent glazing panel, which includes providing a transparent
glass substrate with at least one electrically conductive coating
strip in which heat can be generated by Joule effect. In the method
according to the invention, at least one such strip is formed by
applying onto the substrate a coating composition composed of a
suspension or paste incorporating metal particles all or
substantially all of which are below 5 microns in size, intermixed
with glass particles at least part of which having a softening
point lower than that of the glass composing the substrate, and all
or substantially all of which are likewise below 5 microns in size,
and subsequently firing such applied composition, the metal
particles being present in sufficient proportion in relation to the
glass particles to render the coating strip or strips electrically
conductive.
This method affords the important advantage that electrically
conductive coating strips which have a substantially uniform
conductivity along the length thereof can be formed in a relatively
simple manner, using only one coating deposition step. It follows
that a similarly high standard of uniformity can be attained as
between one conductive coating strip and another formed on the same
panel, or on a different panel in the course of mass production
manufacture.
The observance of the specified conditions in respect of the
granulometry of the applied coating composition is undoubtedly a
factor which contributes to the foregoing advantageous result. In
view of the differences in the specific gravities of metal and
glass, it is surprising that the application of both the metal and
the glass in the form of particles below 5 microns in size does not
prevent the formation of coating strips of substantially uniform
composition. In fact it is that granulometry condition which makes
it possible for coating strips of substantially uniform
conductivity to be easily formed.
Coating compositions hitherto known for forming electrically
conductive coatings incorporate mixtures of metal and glass
particles in which the glass particles cover a size range extending
very much above 5 microns. Contrary to what would be expected on
theoretical grounds, the highest standard of coating uniformity
which can be realized when using such a composition is greatly
inferior to that which can be achieved by using a method according
to the present invention.
The performance of the present invention involves more careful
preparation of the coating constituents in order to observe the
specified granulometry condition, but this step is amply justified
by the greatly improved results which are obtained.
Preferably, the glass particles have substantially the same average
grain size as the metal particles. By observing this further
granulometry condition the standard of uniformity which can be
achieved is optimized.
Avantageously the glass particles in the coating composition are
composed of intermixed particles of two lead borosilicate glasses
of different softening points and the applied composition is fired
to cause at least that one of such glasses which has the lower
softening point to serve as a binder for the metal particles.
The use of different intermixed glasses of different softening
points affords very important advantages. Firstly, the properties
of the coating strips are not determined merely by the metal
particles and one selected glass. The second glass can be selected
to confer on the coating strips a property which the strips would
not otherwise possess.
It is desirable for the coating composition to contain a glass
which can be melted or sufficiently softened for binding the metal
particles without the necessity for excessively high firing
temperatures. When using intermixed glasses of different softening
points, the glass of lower softening point can be selected to serve
as a binder while the higher softening point glass can be selected
to confer some special property on the coating strips, for example
a high abrasion resistance.
Advantageously, the higher softening point glass, which is the
harder glass, is present in a proportion not exceeding 40% by
weight, based on the total weight of the glass mixture, in order to
promote abrasion resistance. It is of course within the scope of
the invention to use a composition in which the proportions of both
glasses in the coating composition and the firing conditions are
such that both glasses serve as binder for the metal particles.
Another advantage of using a mixture of glasses of different
softening points is that, as the properties of the coating strips
are in part dependent on the relative proportions of the different
glasses, a range of properties is attainable by using the different
glasses in different relative proportions.
Preferably at least 10% by weight of the glass having the higher
softening point is constituted by oxides of aluminum and titanium
or of aluminum, titanium and zirconium. The presence of such oxides
in combination in the higher softening point glass has been found
to improve the properties of the coatings, in particular their
hardness and abrasion-resistance.
In certain methods according to the invention, which also yield
coatings with favorably high abrasion resistance, the glass having
the higher softening point includes oxides of aluminum, titanium,
zirconium and cadmium in an aggregate proportion of at least 10% by
weight of such glass.
Preferably the metal particles constitute at least 40% of the
aggregate weight of the metal particles and glass particles. It has
been found that the inclusion of such high proportions of metal
particles, e.g. silver particles, further facilitates the formation
of coatings having a predetermined and substantially uniform
electrical conductivity in repetitive performances of the
method.
Preferably the coating composition contains only a minor proportion
of a liquid vehicle, sufficient to render the composition capable
of being uniformly spread like a paint and the composition is fired
substantially immediately after its application to the panel. By
using a small proportion of liquid vehicle, the need for the
coating strips to be left to dry before commencing the firing step
is obviated. The panel can pass directly from a coating station to
a firing station. This is very important in mass production
manufacture. It is very suitable to use an oil as the liquid
vehicle.
A panel containing a glass substrate which has been provided with
one or more electrically conductive coating strips by a method
according to the invention can be used as such for glazing
purposes, e.g., for forming a vehicle window. Alternatively such
glass panel may be combined with one or more other sheets to form a
laminated or other composite glazing panel. For example, a
protective sheet may be applied over the electrically conductive
coating strip or strips so that such strip or strips are sandwiched
between the glass panel substrate and the protective sheet.
The coating strip, or each coating strip, can be applied by a
serographic technique. This technique involves the use of a screen
which is prepared to form stencil in which the open area or areas
penetrable by the coating composition correspond to the strip-like
zone or zones on which the coating composition is to be
deposited.
The invention also includes a transparent glazing panel composed of
a glass substrate carrying one or more attached electrically
conductive coating strips in which heat can be generated by Joule
effect, in which there is at least one such strip which is composed
of metal particles together with intermixed lead borosilicate
glasses of different softening points, at least the lower softening
point glass serving as binder for such metal particles.
Such a panel has the important advantage that the coating strip has
a combination of properties deriving from the different constituent
glasses. When manufacturing a plurality of such panels the
technical specifications of the coating strips can be modified
quite easily from one panel to another by modifying the relative
proportions of the different glasses in the coating
composition.
In preferred embodiments of the invention the transparent glazing
panel as above defined is one in which all or substantially all of
the metal particles are below 5 microns in size and wherein at
least the higher softening point glass is present in the form of
particles all or substantially all of which are also below 5
microns in size. Such a product is advantageous because by virtue
of the small size of the particles of the higher softening point
glass they can more uniformly influence the properties of the
coating strip or strips. Moreover, in manufacturing such a product
there is even less risk of formation of a conductive strip which is
liable to become locally overheated, than when making a product
which does not satisfy the specified condition. Localized
overheating would rapidly lead to the rupture of the conductive
strip.
In a panel according to the invention as above defined it is
preferable for at least 10% weight of the glass having the higher
softening point to be constituted by oxides of aluminum and
titanium or of aluminum, titanium and zirconium. The advantage of
this feature, and of other preferred features hereafter referred to
will be appreciated from the above discussion of the corresponding
features as applied in a method according to the invention as
hereinbefore defined.
Preferably the glass having the higher softening point is composed
of oxides of aluminum, titanium, zirconium and cadmium in an
aggregate proportion of at least 10% by weight.
In certain panels according to the invention there is at least one
such electrically conductive strip which is composed of silver
particles and such intermixed glasses and which contains such
silver particles in a proportion of at least 40% by weight, based
on the aggregate weight of the silver and glass particles.
In certain panels according to the invention there is at least one
such strip which is composed of such intermixed glasses and less
than 60% by weight of silver particles, and which is locally
over-coated at at least one region by a coating composed of at
least 60% by weight of silver particles. Such over-coating forms a
very satisfactory means of connecting a lead-in wire to the
conductive coating strip. In the case of a panel composed of a
single conductive coating strip, e.g., a strip which follows a
zig-zag course across the panel, these may be two such local
over-coatings, located at or near the opposite ends of the strip.
In the case of a panel composed of a plurality of conductive
coating strips disposed in spaced parallel relationship,
electrically conductive deposits composed of at least 60% by weight
of silver can be formed on strip-like zones running across the
opposed end portions of the parallel strips. Such deposits form
electrodes via which the strips can be connected in parallel to a
source of E.M.F.
A glazing panel according to the invention can be used as a vehicle
window or as part of a vehicle window, e.g., as part of a laminate
which includes a protective sheet covering the electrically
conductive coating strip or strips.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are front views of two glazing panels formed
according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Example 1
A heatable glazing panel for a vehicle rear window and including
electrically conductive strips was manufactured by a serographic
process.
The manufacturing technique was as follows:
Firstly, a photo-sensitive composition was applied onto both faces
of a Nytal screen marketed by Schweiz Seiten Gaze Fabrik, CH 9425
Thal St. Gallen, Switzerland. It is equally suitable to use a
polyester screen of type 11OD manufactured by the same firm.
The photo-sensitive composition was "Tamisol Red" marketed by
Publivenor, 87-91 rue de l'Eglise St. Pierre, 1090 Bruxelles-Jette,
Belgium.
The screen covered by the photo-sensitive composition was exposed
for about a half hour to a light source through a negative image of
the intended pattern of conductive strips. The negative was
constituted by a sheet of glass covered by self-adhesive opaque
sheets along the strip zones. The latent image on the screen was
then developed by soaking the screen in water at about
50.degree.C., which caused removal of the photo-sensitive
composition along the strip zones. This development was followed by
rinsing in water and firing at about 100.degree.C. for about 30
minutes. The screen was then ready for use in the manufacture of
the heatable window.
The developed screen was applied onto a glass sheet substrate
constituting the glazing panel and electrically conductive coating
composition in the form of a paste was forced through the open
meshes of the screen. The paste, which will subsequently be
described, adhered to the glass substrate.
The panel, constituted by the glass substrate covered by the paste
along the strip zones corresponding with the open areas of the
screen, was subjected to a thermal treatment in order to fire the
coating composition. The panel was then cooled and was then ready
for use.
A heatable glazing panel made as above described is illustrated in
FIG. 1. The panel is composed of a sheet substrate 1 made of
sodalime glass of ordinary composition. This sheet measures 750mm
.times. 400mm .times. 5mm. On this sheet two electrodes 2 and 3
have been deposited so as to cover the ends of the eight conductive
strips 4. Each of these strips 4 has a width of 1 mm and a
thickness of 10 microns and is 730 mm in length.
The electrodes 2 and 3 as well as the strips 4 have been formed by
applying to the glass sheet 1, and then firing, a paste obtained by
mixing silver particles less than 5 microns in size with particles
of two glasses of different compositions, the glass particles being
less than 3 microns in size, and adding a liquid vehicle.
One of the glasses, which will hereafter be designated "the binder
glass" and of which the softening point is lower than that of the
other glass, has in this example, the following composition in
percentages by weight: SiO.sub.2, 25.95%; Na.sub.2 O, 1.49%;
K.sub.2 O, 0.61%; CaO, 1.02%; Al.sub.2 O.sub.3 + TiO.sub.2, 8.06%;
BaO, 0.41%; ZrO.sub.2, 1.35%; PbO, 48.03%; B.sub.2 O.sub.3, 13.01%;
MgO, 0.067%.
The other glass has the following composition in percentages by
weight: SiO.sub.2, 28.31%; Na.sub.2 O, 1.72%; K.sub.2 O, 0.73%;
CaO, 0.20%; Al.sub.2 O.sub.3 + TiO.sub.2, 11.41%; Fe.sub.2 O.sub.3,
0.43%; BaO, 0.23%; ZrO.sub.2, 1.68%; PbO, 47.08%; B.sub.2 O.sub.3,
5.06%; CdO, 3.07%; MgO, 0.02%.
The past was composed of the specified different constituents in
the following amounts: 852.4 g silver, 147.6 g of the binder glass,
200 g of the higher softening point glass, and an organic liquid
vehicle of conventional type in an amount of 15% by weight based on
the total weight of the paste.
During the firing of the applied electrically conductive
composition, the liquid vehicle in the paste evaporated and the
binder glass was melted. This binder glass enveloped the particles
of silver and of the higher softening point glass and adhered to
the glass sheet substrate. The panel was then slowly cooled.
The panel manufactured by the above process has important
advantages. When in use, that is to say when an electric current is
passed through the parallel electrically conductive strips in order
to heat them, the strips acquire a temperature which is
substantially uniform along the length of the individual strips and
substantially uniform from one strip to another.
The variation in electrical resistivity along each conductive strip
does not exceed .+-.3% and the variation in electrical resistivity
from one strip to another does not exceed .+-.6%.
Various tests were performed to assess the mechanical resistance of
the coating strips. One test involved applying a ball of tungsten
carbide to the coated surface of the sheet of glass under a force
of 125 grams and displacing the ball to and fro over the surface at
a frequency of 60 cycles per minute, perpendicularly across the
conductive strips, while these were connected to a source of
electrical current at 6 volts. It was found that the electrically
conductive strips became ruptured after from 2000 to 5000 cycles of
the abrasive tool.
A test was also performed to determine the resistance of the
electrically conductive coating strips to impairment by a humid
environment. The test involved maintaining the window at a
temperature of 42.degree.C in an atmosphere of 100% humidty. After
more than 10 days no deterioration of the panel was detected.
Example 2
An electrically heatable glazing panel was manufactured using a
serographic process as described in Example 1. The panel was in all
respects similar to that manufactured in accordance with Example 1
except for the fact that after firing the applied electrically
conductive coating composition the panel was cooled in a current of
gas in order to effect thermal tempering of the glass substrate and
render it more resistant to breakage by thermal shocks.
Example 3
An electrically heatable glazing panel as shown in FIG. 1 was
manufactured by a process similar to that described in Example
1.
The paste applied to the glass sheet substrate 1 for forming the
electrodes 2 and 3 and the conductive strips 4 was composed of, in
parts by weight, 2 parts of nitrocellulose, 25 parts of silver
particles, and 73 parts of a glass having the following composition
in percentages by weight: SiO.sub.2, 8.5%; Al.sub.2 O.sub.3, 10.7%;
CaO, 5.5%; K.sub.2 O, 1.6%; SnO.sub.2, 0.5%; Li.sub.2 O, 1.5%;
Ag.sub.2 O, 49%; B.sub.2 O.sub.3, 22%; Na.sub.2 O, 0.7%.
The silver particles and the particles of glass were all equal to
or less than 3 microns in size.
The conductive strips exhibited only a small variation in
electrical resistivity along their lengths and electrical
resistivities of the different strips were substantially the
same.
Example 4
An electrically heatable glazing panel as shown in FIG. 1 was
manufactured, using a sheet of glass of ordinary composition as the
substrate 1.
The conductive strips 4 were formed by a serographic method. In
order to obtain strips having an aesthetically pleasing appearance,
the serographic screen was placed with its weft threads parallel to
the direction of the electrically conductive strips.
The electrically conductive strips and the electrodes 2 and 3 were
formed by applying, and then firing, a paste having the following
composition by weight: 67.5% gold, 7.5% glass, 25% of an inert
liquid vehicle. The gold and glass were in the form of particles
equal to or smaller than 4 microns in size.
The glass had the following composition by weight:
PbO 75% SiO.sub.2 24% Al.sub.2 O.sub.3 1%
The conductive strips exhibited only a very small variation in
electrical resistivity along their lengths and from one strip to
another, such variation being of the same order as in the panels
formed according to the preceding examples.
Example 5
An electrically heatable glazing panel as shown in FIG. 1 was
manufactured by a process similar to that of Example 1.
The conductive electrodes 2 and 3 and the conductive strips 4 were
formed by applying, and firing, an electrically conductive paste
having the following composition by weight: 80% silver, 10% of a
lead borosilicate glass, 10% of methyl alcohol. The lead
borosilicate glass had the following composition by weight:
75% PbO 6% SiO.sub.2 6% Al.sub.2 O.sub.3 13% B.sub.2 O.sub.3
The silver and the borosilicate glass were in the form of particles
less than 4 microns in size.
The reproducability of electrically conductive strips formed by
means of this paste is very good. The variation in electrical
resistivity along the strips and from one strip to another is very
small, being of the same order as in the panels formed according to
the preceding examples.
Example 6
An electrically heatable glazing panel as shown in FIG. 1 was
manufactured by a process similar to that of Example 1. The
electrodes 2 and 3 and the conductive strip 4 were formed from a
coating composition (applied as a paste) composed of particles of
silver and glass. The silver and glass particles had approximately
the same mean size, the particles sizes being 0-2 microns.
The glass particles included particles of two different glasses as
follows:
Glass No. 1: PbO, 48%; SiO.sub.2, 26%; B.sub.2 O.sub.3, 13%;
Na.sub.2 O, 2%; Al.sub.2 O.sub.3, 5%; TiO.sub.2, 3%; BaO, 0.4%;
ZrO.sub.2, 1%; K.sub.2 O, 0.6%; CaO, 1% (percentages by
weight).
Glass No. 2: PbO, 45.5%; SiO.sub.2, 30%, B.sub.2 O.sub.3, 5%;
Na.sub.2 O, 1.5%, Al.sub.2 O.sub.3, 5.5%; TiO.sub.2, 6.5%;
ZrO.sub.2, 1.7%; K.sub.2 O, 0.2%, CaO, 0.2%; BaO, 0.2%; MgO, 0.2%;
Fe.sub.2 O.sub.3, 0.5%; CdO, 3% (percentages by weight).
The coating composition contained 800 g of silver, 100 g of Glass
No. 1 and 300 g of Glass No. 2.
It was found that the reproducibility of the electrical resistivity
was even better than that obtainable when using the coating
compositions used in the preceding examples and that it was
possible to reduce the thickness and the width of the conductive
strips 4 without rendering it more difficult to reproduce strips
having similar resistivities on a succession of panels. The
variation in the electrical resistivity along each conductive strip
and from one strip and another is about half of that noted in the
panels according to the previous examples.
Example 7
An electrically heatable glazing panel was manufactured according
to Example 6 except that Glass No. 2 had the following composition
by weight: PbO, 46.5%; B.sub.2 O.sub.3, 5%; SiO.sub.2, 30%; K.sub.2
O, 0.2%; CaO, 0.2%; Al.sub.2 O.sub.3, 5.7%; Na.sub.2 O, 1.5%; BaO,
0.2%; TiO.sub.2, 7%; ZrO.sub.2, 2.2%; MgO, 1%; Fe.sub.2 O.sub.3,
0.5%.
The uniformity and reproducibility of the electrical resistivity is
of the same order as that obtained according to Example 6.
Example 8
An electrically heatable glazing panel as shown in FIG. 2 was
manufactured. The components of this panel are designated by the
same reference numeral as the functionally corresponding components
of the panel shown in FIG. 1.
In the panel shown in FIG. 2 each of the electrodes 2 and 3 has a
width of 20 mm.
The conductive paste used for forming the electrodes 2 and 3 and
the conductive strips 4 contained particles of silver, particles of
two glasses and an organic liquid vehicle of conventional type.
The silver particles and the glass particles had a granulometry of
between 0 and 2 microns and were of the same mean size. The
compositions of the two glasses were as set out in Example 1. The
paste was composed of 400 g of silver, 257 g of the lower softening
point glass (the binder glass) and 343 g of the higher softening
point glass, together with the liquid vehicle in a proportion of
15% of the total weight of the paste.
On top of the electrodes 2 and 3, layers 5 were formed by the local
deposit of a paste composed of the same ingredients but in the
following proportions: 800 g silver, 85 g of the binder glass, 115
g of the higher softening point glass and 15% by weight of the
liquid vehicles (based on the total weight of the composition).
The panel was subsequently heated to fire the coating
compositions.
In addition to the fact that a good reproducibility of the
electrical resistivity was realized, the product possesses the
advantage that one can easily solder electrically conductive wires
to the deposited layers 5. For this purpose one can for example use
a lead-tin-silver or lead-tin-cadmium or a lead-tin-indium
alloy.
It is within the scope of the invention to use other compositions
of conductive paste, other screens and other photo-sensitive
compositions. Although reference has been made to the use of a
serographic technique for applying the electrically conductive
compositions it is equally possible to use other techniques for
applying such compositions.
The invention can be applied not only to vehicle glazing panels but
also in the manufacture of electrically heatable glazing panels for
other purposes. A panel according to the invention may comprise
only the substrate sheet which bears the electrically conductive
coating, strip or strips, or it may include one or more other
transparent sheets forming with such substrate a multiple or hollow
panel. The invention may be applied in the manufacture of a vehicle
windshield composed of one or more transparent sheets. A glazing
panel according to the invention may include one or more glass
sheets, and/or may incorporate a radio antenna and/or an alarm
device for anti-theft or other purposes.
It will be understood that the above description of the present
invention is susceptible to various modifications, changes and
adaptations, and the same are intended to be comprehended within
the meaning and range of equivalents of the appended claims.
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