U.S. patent number 3,694,627 [Application Number 05/100,874] was granted by the patent office on 1972-09-26 for heating element & method of making.
This patent grant is currently assigned to Whirlpool Corporation. Invention is credited to John K. Blatchford, Jan C. Burda, Edward C. Peterson.
United States Patent |
3,694,627 |
Blatchford , et al. |
September 26, 1972 |
HEATING ELEMENT & METHOD OF MAKING
Abstract
A method of making a heating element such as a heating panel for
an oven or other heating device comprising applying to a heat
resistant base such as a metal panel a fired vitreous ceramic first
coating, then applying over this first coating a fired vitreous
ceramic second coating containing dispersed metal particles and
then applying over this second coating a plating of metal
chemically bonded to metal particles contained in the second
coating and then applying over the metal plating a fired vitreous
ceramic protective coating with the result that there is provided
an electrically conducting resistant heating layer that is
protected by the ceramic protective coating. The disclosure also
includes the heating element so produced.
Inventors: |
Blatchford; John K. (St.
Joseph, MI), Peterson; Edward C. (Benton Harbor, MI),
Burda; Jan C. (Eau CLaire, MI) |
Assignee: |
Whirlpool Corporation
(N/A)
|
Family
ID: |
22281975 |
Appl.
No.: |
05/100,874 |
Filed: |
December 23, 1970 |
Current U.S.
Class: |
219/543;
392/435 |
Current CPC
Class: |
H05B
3/262 (20130101); H05B 2203/003 (20130101) |
Current International
Class: |
H05B
3/22 (20060101); H05B 3/26 (20060101); H05b
003/10 (); B44d 001/18 () |
Field of
Search: |
;117/217,212,7A
;219/543,549 ;338/308,309 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Leavitt; Alfred L.
Assistant Examiner: Weiffenbach; Cameron K.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A heating element, comprising: a heat resistant base; fixed
thereto a fired vitreous ceramic coating containing dispersed metal
particles; a plating metal layer in contact with metal particles in
said coating, said metal particles being present in sufficient
quantity to nucleate said plating metal layer; and an overlying
fired vitreous ceramic protective coating.
2. The heating element of claim 1 wherein said heat resistant base
comprises a metal panel having a pair of opposite surfaces, a first
coating is fixed to both said surfaces, and said coating containing
said metal particles is fixed to one only of said first
coatings.
3. The method of making an electrical resistance heating element,
comprising: applying to a heat resistant base a fired vitreous
ceramic coating containing dispersed metal particles; treating the
coating so that it will accept a layer of metal deposited by
electroless metal deposition; and applying over said ceramic
coating by electroless metal deposition a layer of metal.
4. The method of claim 3 wherein the treatment applied to said
coating comprises partial removal of surface portions to increase
surface exposure of said metal particles in said coating.
5. The method of claim 3 wherein said coating is partially fired to
provide a porous surface to receive said metal layer and the
treatment applied to said coating comprises sensitizing and
activating the surface of said coating.
6. The method of making a heating element, comprising: applying to
a heat resistant base a fired vitreous ceramic first coating;
applying over said first coating a fired vitreous ceramic second
coating containing dispersed metal particles; plating over said
second coating a metal layer in contact with metal particles in
said second coating, said metal particles being present in
sufficient quantity to nucleate said plating metal layer; and
applying over said plating metal layer a fired vitreous ceramic
protective coating.
7. The method of claim 1 wherein said dispersed metal particles are
protected from oxidation by incorporating in said vitreous ceramic
second coating prior to firing a reducing agent activated during
the firing of said second coating to minimize oxidation of the
metal particles.
8. The method of claim 1 wherein said heat resistant base comprises
a metal panel having a pair of opposite surfaces, said first
coating is applied to both said surfaces, and said second coating
is applied to one of said first coatings.
9. The method of claim 1 wherein said second coating is partially
removed to increase the surface exposure of said particles prior to
applying said metal layer.
Description
SUMMARY OF THE INVENTION
One of the features of this invention is to provide a method of
making an improved heating element in which the heating member
comprises a protected layer that is electrically conducting to
function as a resistance heating element on a heat resistant
support base.
Other features and advantages of the invention will be apparent
from the following description of certain embodiments thereof taken
in conjunction with the accompanying drawings. Of the drawings:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary sectional view through a portion of a
heating element embodying the invention with the layers thereof
being magnified for clarity of illustration.
FIG. 2 is a fragmentary plan view of the heating element of FIG.
1.
FIG. 3 is a plan view of a second embodiment of the invention with
the protective coating partly removed to illustrate details.
FIG. 4 is a view similar to FIG. 1 but illustrating another
embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In preparing the heating element of the embodiment of FIG. 1 there
is first provided a heat resistant base which may advantageously be
a metal panel, for example, where the heating element 9 is to be
used as an inner surface heating element in a cooking oven. Other
applications include heated panels, heating utensils, heated
counter tops, dryers, water heaters, space heaters and electric
ranges.
The heat resistant base for heating element 9 could be ceramic
instead of metal provided it was strong enough for the intended
application.
In one embodiment the base comprises a sheet steel panel 10. This
metal panel 10 is coated on both sides with a first coating 11 and
12 of a fired on porcelain or other ceramic coating. Next, over one
of these first coatings 11 there is applied a fired vitreous
ceramic second coating 13 containing dispersed metal particles such
as nickel particles distributed throughout with provision of enough
particles to nucleate the plating applied to coating 13. While
nickel particles were utilized in the embodiment of FIGS. 1 and 2,
particles of copper, silver, or chromium-nickel could also be used.
For coating 13 a useful composition has been found to be about 60%
nickel to 40 percent porcelain, both by weight. In this composition
Raney Nickel No. 28, a product of W. R. Grace & Company, Raney
Catalyst Division, was used. Other nickels that can be used are
Mond Nickel Powder Grade 128 MNP 696, average particle size 7-9
microns, a product of International Nickel Company (Mond) Ltd.,
London, England; and Nichrome Powder (Ni 80%; CR 20%) particle size
less than 150 microns, a product of Varlacoid Chemical Company,
Elizabeth, New Jersey. Other metals can also be used. Iron and
cobalt can be used. Gold, platinum and palladium can also be
used.
An example of the preparation of a nickel containing porcelain
enamel slip is as follows: 100 grams of porcelain enamel slip (60
percent solids 40 percent water) and 67.5 g. Raney Nickel No. 28
containing 37.5 percent water was mixed in a Waring Blender for 3-5
minutes. Potassium Nitrite in water was added until the mixture was
the proper consistency for spraying. The nickel containing slip was
then sprayed on a porcelain enameled steel panel in a layer of
about 1 mil thick, dried and fired in a furnace for approximately
three minutes at a temperature of 1,500.degree.F.
It has been found desirable to add a reducing agent such as sodium
hypophosphite (NaH.sub.2 PO.sub.2), sodium borohydride (NaBH.sub.4)
or stannous oxide (SnO), in the amount of 1 percent to 10 percent
by weight of the porcelain enamel slip used in the coating, to the
material of the metal particle containing coating 13, and to the
vitreous ceramic coating 15 referred to below, before the firing of
these coatings. The addition of a reducing agent to the wet slip of
coating 13 prevents excessive oxidation of the metal of coating 13
during such firing.
Next, in a preferred embodiment, there is applied to this second
coating a metal layer 14 in contact with the metal particles of the
coating 13. The metal particles of the coating 13 need not be
present in sufficient quantity to provide an electrically
conductive layer themselves. However, coating 13 must contain
enough metal particles to nucleate the plating or application of
metal layer 14. The metal layer here may be nickel and is
preferably applied by the well known electroless metal deposition
process which involves chemical deposition of an adherent metal
coating to the second coating substrate in the absence of an
external electric source.
The utilization of porcelain coatings 11 and 12 is not essential
providing that the metal particles in the layer adjacent the metal
panel 10 are sufficient to give nucleating sites for the
electroless plating to form metal layer 14, but insufficient to
give a conductive layer after firing.
In one method of applying the metal coating 14 the exposed surface
of the particle containing coating 13 is abraded as with sand paper
in order to expose metal particles.
Another way of exposing these metal particles is by chemical
etching of which examples of etching solution are 1 percent
hydrofluoric acid in water applied for 2 or 3 minutes, 2 percent by
volume of sulfuric acid in water applied for the necessary time up
to 10 minutes, or 4 percent phosphoric acid by volume in water for
the necessary time up to 20 minutes. These times will of course
vary in the well known manner depending upon the type of porcelain
used.
When thusly exposed the metal such as nickel layer 14 is chemically
bonded to the exposed nickel particles. This bonding provides
secure anchoring of the metal layer to the porcelain layer 13
thereby providing considerable mechanical strength. Another very
important advantage is that the chemically bonded metal film when
heated electrically during use provides good distribution of heat
as the particles that are bonded to the metal layer distribute heat
throughout the panel structure. This results in a lower temperature
of operation of the nickel layer. The bonding of the metal such as
nickel layer 14 to the metal particles in layer 13 improves heat
transfer throughout the heating element, thereby reducing the
possibility of developing hot spots or overheated areas with
subsequent burn out.
An alternate method of applying the plated metal layer 14 is set
forth below. Just prior to plating metal layer 14 the area of the
metal panel containing the second coating 13 is sensitized as
follows: The area of the metal panel containing coating 13 is well
cleaned, and then the well cleaned surface is coated with an
aqueous solution containing 10 g/liter stannous chloride dihydrate
(SnCl.sub.2.sup. . 2H.sub.2 O) and 40 ml/liter concentrated
hydrochloric acid (37% HCl) for one minute. The solution is rinsed
off well with water and the surface coated with an aqueous solution
containing 0.3 g/liter palladium chloride (PdCl.sub.2) and 3.0
ml/liter concentrated hydrochloric acid (37% HCl) for 1 minute. The
last step with the palladium chloride solution is called
activating. Platinum chloride can also be used for activation.
Sodium hypophosphite and a hydrazine solution can also be used for
sensitizing.
After sensitizing and activating the metal plating by the
electroless metal deposition process as described above may then be
accomplished in a very short time which may be as little as 2
minutes.
After the metal layer 14 has been deposited, there is applied an
overlying fired vitreous ceramic protective coating 15 that covers
the metal layer 14 (except at terminal portions thereof as
described below) and provides protection to metal layer 14.
The fired ceramic coatings 11, 12, 13 and 15 may be porcelain. The
ceramics of the various layers may be the same or may be
different.
As stated above, coating 15 should preferably include a reducing
agent and the addition of such reducing agent minimizes oxidation
of metal layer 14 during the firing of layer 15.
For low temperature applications, where metal layer 14 does not
reach a temperature high enough for an objectionably rapid rate of
oxidation to take place, protective coating 15 may be omitted.
An electric current may be conducted through the metal layer 14 by
electric terminals 16 and 17 affixed to metal layer 14 at opposite
ends of the heating element. In one embodiment the terminals 16 and
17 were provided by applying a layer of silver paint to the
opposite ends of metal layer 14. A suitable silver paint for
terminals 16 and 17 is Engelhard Industries, Inc., Hanovia Liquid
Gold Division, Squeegee Organic Silver No. 9124.
In FIG. 2 a portion of coating 15 is removed to illustrate the
relationship of electrically conductive metal layer 14 to the
underlying metal particle containing coating 13. Additionally, FIG.
2 illustrates that protective coating 15 partially overlies edge
portions of terminals 16 and 17 for added protection for the edge
portions of the terminals.
In some applications the voltage specifications of the current
source or other reasons may make it advantageous to provide a
heating element 9a with a metal layer 14a in the form of a
serpentine path as illustrated in FIG. 3. The serpentine path is
obtained by dipping or spraying over a porcelain enamel coating on
a steel panel a conventional photosensitive resist material and
then hardening and baking the resist in the absence of ultraviolet
light.
Then, using a photographic negative in which the black areas are
the serpentine path areas to be plated, the photo resist coated
panel is exposed to ultraviolet light through the negative.
The photo resist is selectively removed from those areas not
receiving light by washing the exposed panel with a developing
agent which will remove the photo resist.
After a short bake to harden the photo resist the exposed areas are
plated by the electroless metal deposition process referred to
above. The unwanted photo resist material along with any plating
that has occurred on it is then removed with a suitable photo
resist remover.
An alternative method to obtain the serpentine path is to use a
positive photographic film having the desired serpentine path image
in the exposure process on a panel which has been plated with
nickel prior to coating with photo resist. Then the nickel layer in
the unwanted areas is etched away with an etching solution such as
nitric acid.
The end portions of serpentine metal layer 14a may advantageously
be enlarged to form terminals as indicated at 17a. Heating element
9a may then be coated with a protective fired vitreous ceramic
coating 15a.
FIG. 4 is similar to the FIG. 1 embodiment in that there is also
provided a heat resistant base 18 which may be a metal panel and a
fired vitreous ceramic first coating 19 and 20 as indicated in FIG.
4. Then on one of these coatings 19 there is sprayed a masked area
of porcelain enamel slip. The porcelain enamel slip particles need
not contain dispersed metal particles since the porcelain coating
will accept a layer of metal deposited by electroless metal
deposition following treating of the coating as described
below.
The mask is removed and the dried porcelain enamel slip or bisque
is partially fired to provide a coating 21 having a porous surface.
This porous surface is activated with stannous chloride solution,
washed, and sensitized with a palladium chloride solution as
described above and then electroless metal plated using nickel, for
example, to give a nickel layer 22 capable of being heated
electrically. The porosity of the surface of coating 21 facilitates
the plating process by providing indentations in which the nickel
is received providing positive adhesion between coating 21 and
metal layer 22. A cover coat of porcelain enamel 23 is applied over
the nickel layer 22 leaving exposed areas (not shown) at each end
which may be coated with a silver paint and used as the terminal
connections similar to the terminals 16 and 17 of FIGS. 1 and
2.
Having described our invention as related to the embodiments
disclosed in the accompanying drawings, it is our intention that
the invention be not limited by any of the details of description,
unless otherwise specified, but rather be construed broadly within
its spirit and scope as set out in the accompanying claims.
* * * * *