U.S. patent number 3,922,452 [Application Number 05/449,896] was granted by the patent office on 1975-11-25 for microwave browning vessel.
This patent grant is currently assigned to Corning Glass Works. Invention is credited to Ray B. Forker, Jr., Joseph N. Panzarino.
United States Patent |
3,922,452 |
Forker, Jr. , et
al. |
November 25, 1975 |
Microwave browning vessel
Abstract
Browning vessels to be used with microwave ovens which comprise
electroconductive films demonstrating improved detergent durability
are described. The durable films provide stable resistance heating
characteristics over a longer period, extending the useful lifetime
of the browning vessel.
Inventors: |
Forker, Jr.; Ray B.
(Horseheads, NY), Panzarino; Joseph N. (Big Flats, NY) |
Assignee: |
Corning Glass Works (Corning,
NY)
|
Family
ID: |
23785915 |
Appl.
No.: |
05/449,896 |
Filed: |
March 11, 1974 |
Current U.S.
Class: |
428/34.6;
427/106; 428/210; 219/725; 252/520.1; 427/126.2 |
Current CPC
Class: |
H05B
6/6494 (20130101); A47J 36/02 (20130101); Y10T
428/24926 (20150115); Y10T 428/1317 (20150115) |
Current International
Class: |
A47J
36/02 (20060101); H05B 6/64 (20060101); B65D
001/00 () |
Field of
Search: |
;117/201,211,229
;252/518 ;219/10.55 ;428/35,210 ;427/106,126 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weinblate; Mayer
Attorney, Agent or Firm: VAN DER Sterre; Kees Janes, Jr.;
Clinton S. Patty, Jr.; Clarence R.
Claims
We claim:
1. A microwave browning vessel demonstrating improved detergent
durability and increased service life consisting of a glass-ceramic
vessel having on at least a portion of the surface thereof an
electrically conductive film consisting at least predominately of
tin oxide, said glass-ceramic vessel being formed of a
glass-ceramic material which exhibits a weight loss due to acid
leaching of less than about 0.2 milligrams of material per square
centimeter of leached surface area upon exposure of the leached
surface area to an aqueous 5 weight percent solution of
hydrochloric acid at 95.degree.C. for 24 hours.
2. A microwave browning vessel according to claim 1 wherein the
glass-ceramic material is of lithium aluminosilicate composition
and comprises a beta-spodumene/beta-eucryptite solid solution as
the principal cyrstal phase.
3. A microwave browning vessel according to claim 1 wherein the
electrically-conductive film consists essentially of tin oxide and
antimony oxide (Sb.sub.2 O.sub.3), said antimony oxide being
present in an amount of about 0.001-13 percent by weight.
Description
BACKGROUND OF THE INVENTION
Microwave cooking provides a rapid and efficient means of
processing foodstuffs, but generally does not result in surface
browning of the food. To provide the surface browning which is in
many cases preferred, some form of direct surface heating, either
by contact or irradiation is required.
Conventional means of providing browning with microwave energy
typically comprise the use of a microwave-heatable apparatus in the
microwave chamber which acts as a supplemental heating source to
brown the food by irradiation or contact. Such an apparatus is
rendered microwave-heatable through the incorporation therein of
electroconductive members which are heated by internal currents
generated by the microwave field.
A preferred form of microwave browning apparatus is a browning
vessel such as a plate, platter, dish or pan composed of a glass,
glass-ceramic or ceramic material to which has beeen applied an
electroconductive tin oxide film. The film typically has an
electrical resistance value in the range of 90-350 ohms per square
which renders it efficiently heatable in a microwave field. Upon
exposure to microwave energy, the film and subsequently the vessel
are heated to a degree sufficient to brown the food by contact.
U.S. Pat. No. 3,783,220 describes a microwave browning vessel of
this type, consisting of a glass, ceramic or crystallized glass
(glass-ceramic) vessel having on its exterior surface a thin
electroconductive coating of tin oxide. Tin oxide films such as
described in U.S. Pat. No. 3,564,706 to Mochel, consisting
predominately of tin oxide but also containing about
0.001-13percent Sb.sub.2 O.sub.3 by weight, are also suitable for
this application.
Microwave browning vessels of the kind described in the
aforementioned patent have recently become available commercially
and initially provide an acceptable solution to the problem of
browning with microwave energy. However, sustained usage of
commercially available browning vessels of this type has uncovered
a service life problem, apparently associated with the stability of
the electroconductive tin oxide film, wherein a premature
deterioration in the resistance heating characteristics of the film
is observed. This deterioration in heating characteristics means
that longer and longer heating times and increased quantities of
microwave energy are required to obtain the desired browning
performance. In many cases, the erratic electrical behavior of
degraded films ultimately causes vessel failures through localized
melting or fracture. We have recently discoverd that this problem
is largely attributable to poor detergent durability demonstrated
by the electroconductive tin oxide film on commercially available
ware. Hence, accelerated service testing of commercially available
ware with strong detergents produces rapid deterioration of the tin
oxide film and erratic electrical resistance characteristics.
Examination of this service-tested ware reveals a tin oxide film
characterized by high resistivity and film defects, including
spalled areas and pinhole clusters which are likely sources of the
electrical arcing which is responsible for catastrophic vessel
failures. Similar defects are demonstrated by films on ware
subjected to prolonged periods of actual use.
Our attempts to improve the detergent durability of conventional
tin oxide films by modifying the composition of the films and/or
the method by which the films are deposited on the glass-ceramic
vessels have not been entirely successful. Tin oxide films are
normally applied to ceramic substrates by a process comprising
heating the substrates to an elevated temperature and spraying the
heated substrates with a solution of a thermally decomposable tin
compound. Upon contact with the heated substrate, the solvent is
volatilized and the tin compound is decomposed to yield an integral
tin oxide coating which is electrically conductive. Although
variations in substrate temperature, spraying method, solvent
composition, tin compound composition, and, within limits, film
thickness, have been attempted, no modifications have been
discovered which are entirely effective to improve the detergent
durability of these films. Nor have any composition additives been
found which act to improve the tin oxide film durability.
SUMMARY OF THE INVENTION
We have now discovered that the low detergent durability of tin
oxide films employed as above described is not due to any inherent
weakness in the films, but rather is somehow related to the problem
of bonding the film to the substrate. Hence, we believe that the
poor detergent durability of prior art tin oxide-coated
glass-ceramic browning dishes is largely attributable to bonding
defects between the film and the glass-ceramic substrate, with
respect to which the chemical nature of the glass-ceramic
supporting surface plays a major role. Based on this discovery, we
have been able to produce glass-ceramic browning vessels such as
plates, dishes, pans and the like having electrically conductive
tin oxide films of greatly improved detergent durability by
selecting glass-ceramic substrate materials having surfaces which
meet specified minimum requirements of chemical stability. The
practical effect of our durable film-substrate combination is a
microwave browning vessel offering stable resistance-heating
characteristics over a significantly prolonged period of use.
The precise nature of the substrate instability giving rise to poor
detergent durability in the subsequently applied tin oxide film is
not completely understood. It appears certain that low detergent
durability on the part of the glass-ceramic substrate is not a
principal cause. Detergent attack is generally attributed to the
alkalinity of detergent solutions, yet durable tin oxide films may
be produced on glass-ceramic substrate materials demonstrating poor
resistance to alkaline attack as well as on substrates having good
alkali durability.
Our present belief is that the surface alkali ion mobility of the
glass-ceramic substrate is an important factor limiting the
durability of tin oxide films conventionally applied thereto.
Hence, we have found that glass-ceramic substrate surfaces
exhibiting low alkali ion mobility, as evidenced by a low degree of
surface leachability in acidic media, provide supporting bases
capable of providing a highly durable tin oxide film. On the other
hand, glass-ceramic surfaces exhibiting high degree of alkali ion
mobility provide bases which appear to reduce the detergent
durability of supported tin oxide films to unacceptably low levels.
It has been suggested that surfaces of high alkali ion mobility
inhibit tin oxide bonding or lead to greater "pinholing" in the
resultant film; however, the exact mode of film failure under
alkaline conditions has not been determined.
The selection of glass-ceramic substrate materials suitable for
incorporation into the browning vessels of the present invention is
based on a determination of the acid leachability of the surfaces
of candidate glass-ceramic materials, which is thought to be a
function of the mobility of the alkali ions therein. Glass-ceramic
materials exhibiting a weight loss due to leaching in a standard
acid solution at a standard temperature over a fixed time interval
of less than a specified weight per square centimeter of surface
area have been found to be excellent materials for the production
of improved tin oxide-coated microwave browning vessels according
to the invention. Glass-ceramic materials exhibiting substantially
greater weight losses due to acid leaching under equivalent
conditions, on the other hand, produce browning vessels of poorer
detergent durability and reduced service life.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A simple test for determining the suitability of glass-ceramic
materials to be incorporated into browning vessels according to the
present invention comprises exposing sample pieces of candidate
materials to an aqueous five weight percent solution of
hydrochloric acid (5 grams HCl per 100 grams HCl solution) at
95.degree.C. for 24 hours. The surface areas of the sample pieces
are determined prior to acid treatment and the samples are weighed
before and after treatment so that the weight loss per unit surface
area of each sample due to acid leaching may be calculated. The
resulting value, expressed as a weight loss in milligrams per
square centimeter of glass-ceramic surface area exposed to the
leaching solution, provides a useful measure of the acid
leachability of a material and thus its suitability for use as a
tin-oxide coated microwave browning vessel. We have found that
glass-ceramic materials exhibiting a weight loss due to acid
leaching of less than about 0.2 milligrams of material per square
centimeter of leached surface area upon exposure to an aqueous 5
weight percent solution of hydrochloric acid at 95.degree.C. for 24
hours provide useful supports for tin oxide coatings and are
desirable constituents of microwave browning vessels according to
the invention. In contrast, glass-ceramic materials exhibiting
significantly greater losses under equivalent conditions, e.g.,
0.28-0.30 milligrams or more per square centimeter of leached
surface area, are found to provide supported tin oxide surface
films of markedly inferior detergent durability.
The testing procedure above described is important to the invention
because it provides a screening method which is dependent only on
the surface characteristics of the glass-ceramic material being
tested. Unfortunately, these surface characteristics may not be
readily predicted in advance merely on the basis of the composition
of a candidate glass-ceramic or the identity of its principal
crystalline phase, since other factors such as nucleation mode and
heat treatment affect the extent of crystallization, the
composition and configuration of residual glassy phases, and other
variables which ultimately control the acid leachability of the
glass-ceramic surface. For example, lithium alumino-silicate
glass-ceramics comprising beta-spodumene and and beta-eucryptite
solid solution crystal phases are widely used to fabricate cooking
vessels because they are significantly stronger than glass and
provide greatly superior thermal shock resistance; however, whereas
some lithium aluminosilicate glass-ceramic materials demonstrate
very low acid leachability so as to provide excellent components of
browning vessels according to the invention, other such materials
exhibit extensive acid leachability and provide browning vessels of
poor detergent durability and abbreviated service life. Thus a
screening method which provides direct information about the
surface characteristics of the material is the best way of
selecting glass-ceramic substrate materials useful for the purposes
of our invention.
The wide variation in acid leachability demonstrated by some
commercially available glass-ceramic materials is demonstrated by
the data set forth in the Table below. The data shown was generated
by preparing small samples of glass-ceramic materials, determining
the weight and surface area of each sample, totally immersing each
sample in an aqueous 5 weight percent solution of hydrochloric acid
at 95.degree.C. for a 24 hour period, removing each sample from
solution, rinsing in distilled water, drying at 140.degree.C. for
1/2 hour, and finally re-weighing each sample to determine the
weight loss per unit surface area incurred during leaching.
Concurrently, alternate samples of the same glass-ceramic materials
are provided with electrically conductive tin oxide films having
thicknesses and film resistivities suitable for microwave heating,
and these tin-oxide-coated materials are subjected to an
accelerated detergent test simulating an extended period of actual
use wherein they are immersed in an aqueous detergent solution
containing 1200 cc of water, 45 grams of sodium hydroxide, and 45
grams of SUPER SOILAX detergent, a commercially available
detergent, at 95.degree.C. for about 40-45 minutes. Following
exposure to this solution the samples are removed and the quality
of the tin oxide films is evaluated.
The Table sets forth a designation for each sample, the general
type of glass-ceramic material comprising the sample, the acid
leachability of each sample, expressed in milligrams of weight loss
per square centimeter of sample surface area upon exposure to the
5percent by weight HCl solution at 95.degree.C. for 24 hours, and
the effect of the accelerated detergent test on the electrically
conductive tin oxide films with which the alternate samples were
provided. Evaluation of the tin oxide films involves coating then
with DY-CHEK dye penetrant, a commercially available dying
composition, and then attempting removal of the dye by various
means. The quality of the tin oxide films is then rated on a film
quality scale according to the ease of removability of the dye as
follows: AA--readily removable with a dry cloth; A--removable with
a wet cloth; B--removable by scouring with abrasive detergent
compositions; and C--not removable by conventional cleaning means
(gross film defects). AA and A indicate excellent film quality and
integrity. B indicates some opening of film structure and shorter
effective life. C indicates potential vessel/coating failure
conditions are present.
TABLE
__________________________________________________________________________
Detergent Test Results Acid Leachability Glass-Ceramic 5%
HCl-95.degree.C.-24 hrs. SnO.sub.2 Film Sample Designation
Glass-Ceramic Material Type (mg/cm.sup.2) Quality Time in
__________________________________________________________________________
Test Corning Code 9608 beta-spodumene/beta-eucryptite ss 0.12 A 40
minutes (TiO.sub.2 -nucleated) Corning Code 9617
beta-spodumene/beta-eucryptite ss 0.01 A 40 minutes (TiO.sub.2
-nucleated) Hercuvit 106 beta-spodumene/beta-eucryptite ss 0.01 A
45 minutes Glass-Ceramic (ZrO.sub.2 -TiO.sub.2 -nucleated) Corning
Code 0336 beta-spodumene/beta-eucryptite ss 0.30 B 40 minutes
(TiO.sub.2 -nucleated) Glass-Ceramic A.sup.1
beta-spodumene/beta-eucryptite ss 1.8 C 40 minutes (ZrO.sub.2
-TiO.sub.2 -nucleated) Glass-Ceramic B.sup.2
beta-spodumene/beta-eucryptite ss 24.0 C 45 minutes
__________________________________________________________________________
.sup.1 Glass-Ceramic A is a material used in the fabrication of
microwave browning vessels which are presently commercially
available. .sup.2 Glass-Ceramic B is a material used in the
fabrication of cooking vessels which are not presently commercially
available.
From the above data, the correlation between the surface
characteristics of glass-ceramic materials as reflected by their
HCl acid leachability and the detergent durability of
electrically-conductive tin oxide films deposited thereon is
readily apparent.
Although the quantitative data in the Table has been set forth only
with respect to beta-spodumene/beta-eucryptite solid solution
glass-ceramics, the same correlation holds in other glass-ceramic
systems, and even in glass systems as evidenced by the fact that
certain glasses having low surface acid leachability provide
chemically suitable supports for the production of highly durable
tin oxide coatings.
The effects of low durability in the tin oxide film on the
performance characteristics of glass-ceramic browning vessels and
the advantages of the present invention as related to improved
vessel performance are shown in more detail in the following
examples.
EXAMPLE I (Prior Art)
A glass-ceramic microwave browning vessel of the commercially
available type, consisting of a glass-ceramic dish having a base
provided with an electrically conductive tin oxide film exhibiting
resistance characteristics suitable for efficient heating by
microwave energy, is selected for testing. The glass-ceramic dish
is composed of Glass-Ceramic A of the above Table, a glass-ceramic
material having a beta-spodumene/beta-eucryptite crystal phase and
moderately high acid leachability, exhibiting a weight loss of
about 1.8 milligrams per square centimeter of surface area upon
exposure to a 5 weight percent hydrochloric acid solution at
95.degree.C. for 24 hours.
This microwave browning vessel is subjected to an accelerated
detergent test comprising immersion in an aqueous detergent
solution containing 0.30percent by weight of SUPER SOILAX
detergent, a commercially-available detergent, at 95.degree.C. This
test has been found to duplicate in a few days the effects on glass
and glass-ceramic cooking articles of several years of use in
actual dishwasher service. The microwave browning vessel is
periodically removed from this detergent solution and the tin oxide
film is examined for evidence of deterioration.
At the end of 36 hours of exposure to the detergent solution,
examination of the selected browning vessel reveals localized
spalling of the tin oxide coating from the glass-ceramic vessel,
particularly at locations where the coating is thin. Testing of the
coating by dye application and removal indicates the additional
presence of pinhole defects clustered at numerous locations
throughout the coated area. The dye is not removable from many of
these coating defects, indicating a rating of C on the
aforementioned film quality scale.
This browning vessel with its deteriorated tin oxide coating is
placed in a microwave oven to determine the effects of coating
degradation on heating performance. As the oven is activated, some
electrical arcing is observed in the tin oxide coating. After a
short heating interval, breakage of the glass-ceramic vessel
occurs. This breakage is attributed to large thermal gradients
induced in the glass-ceramic vessel because of the extreme
non-uniformity of heating exhibited by the degraded tin oxide
film.
This example illustrates only one failure mode which has been
observed in glass-ceramic browning vessels having tin oxide films
of poor electrical uniformity; breakage of the vessel on cooling
after use has also been observed in some cases. In addition, the
electrical arcing observed in deteriorated tin oxide films is
detrimental even when vessel failure does not result because it can
cause damage to microwave oven components.
EXAMPLE II
A glass-ceramic cooking vessel composed of a glass-ceramic material
having a weight loss on exposure to aqueous 5 weight percent HCl at
95.degree.C. for 24 hours of less than 0.2 milligrams per square
centimeter is selected for treatment. This vessel is composed of
Corning Code 9608 glass-ceramic material, a material described in
the above Table as a beta-spodumene/beta-eucryptite glass-ceramic
material exhibiting a weight loss on acid leaching of about 0.12
milligrams per square centimeter under the conditions described. An
electrically conductive tin oxide film exhibiting resistance
characteristics suitable for efficient heating by microwave energy
is provided on the base portion of the vessel by conventional
means. The microwave heating characteristics of this vessel are
equivalent to the initial heating characteristics of browning
vessels of the commercially available type described in Example I
above.
The glass-ceramic browning vessel prepared as described is
subjected to the accelerated detergent test described in Example I,
wherein it is immersed in an aqueous detergent solution containing
0.3 percent by weight of SUPER SOILAX detergent at 95.degree.C. The
vessel is periodically removed from the detergent solution,
examined for film defects, and returned to solution.
After a total immersion time of 120 hours in the detergent
solution, the vessel is removed and examined for tin oxide film
defects by dye application and removal as herein above described.
The film defects present are such that the dye is readily removed
from the film by rubbing with a wet cloth indicating a rating of A
using the aforementioned scale.
The browning vessel detergent-tested as above described is then
placed in a microwave oven to evaluate the heating performance of
the tin oxide film. Heating is rapid and uniform and no electrical
arcing of any kind is observed. It is therefore concluded that the
vessel would provide extended service in actual use under detergent
dishwashing conditions.
The browning vessel of Example II comprises the best mode presently
known for carrying out the present invention. Vessels composed of
Corning Code 9608 glass-ceramic material are commercially available
as Corning-ware skillets or pots and may be coated with
electricallyconductive tin oxide films according to conventional
methods to provide browning vessels offering improved tin oxide
detergent durability and resistance heating characteristics
substantially more stable than are provided by glass-ceramic
browning vessels available in the prior art.
While the invention has been described with reference to the
manufacture of microwave browning vessels having electroconductive
tin oxide films of improved detergent durability, it is expected
that the selection of glass-ceramic substrates as hereinabove set
forth would permit the manufacture of improved microwave browning
vessels wherein electroconductive films composed of other oxides
such as indium oxide or other conductive materials such as carbon
are alternatively employed.
* * * * *