Background Of Invention In certain oven cooking applications it is advantageous to have a coating on the inside of the oven cavity that reflects radiant energy. Unfortunately, most coating materials exhibit characteristics which are not ideal for the reflection of radiant energy or energy characterized by infrared radiation. Generally, the absorption characteristics of most coatings have not been engineered to achieve a high degree of reflectivity.

Additionally, the matrix or body of the coating may have an overriding effect on the reflectivity of the coating.

Enhanced thermal reflectivity of a coating over a range of wave lengths has a number of important benefits in certain applications. These include better thermal management in devices used to process any variety of materials via heating, such as, for example, an oven that is utilized to cook food.

Porcelain enamel coating materials are well-known and used extensively to coat the interiors of heating devices such as ovens. Examples of such porcelain enamel

coating materials and methods for applying such coatings may be found for example in U.S. Patent Nos. 4,204,021, 4,110,487, 4,085,021 and 3,928,668.

Unfortunately, the ability of conventional porcelain enamel coating materials to reflect radiation is minimal.

Summarv Of Invention The present invention provides a new and improved porcelain enamel coating composition that affords a high degree of infrared reflectivity. The coating composition of the present invention is especially well-suited for use in connection with cooking appliances.

In a preferred embodiment the reflective porcelain enamel coating material of the present invention comprises a glass component and a separate and distinct addition of cerium oxide. The glass component includes a composition by weight of from about 0 to 20% Awl203, 0to20% BaO, 0-30% B2O3, 0-30% CaO, 0-20% K2O, 0-15 % Li2O, 0-20% Na2O, 0-20% P2O5, 0-30% Sb203, 10-60% SiO2, 0-30% TiO2, 0-20% ZnO, 0- 20% ZrO2, 0-5% CeO2 and 0-10% F. The glass component may comprise one or more glass frits so as to provide this overall stated composition. The cerium oxide, which is added, for example, as a mill addition with the glass component, preferably is contained within the composition at a rate by weight percent of from about 0.20 % to about 3.0%.

The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative,

however, of but a few of the various ways in which the principles of the present invention may be employed.

Detailed Description The novel porcelain enamel compositions of the present invention are prepared by including based on the weight of the total composition from about 0.20% to about 3.0% by weight cerium oxide in the composition. This level of cerium oxide is separate from any cerium oxide that may be present in the glass component of the composition. The separate and distinct addition of cerium oxide to the composition appears to provide a distinct advantage. Specifically, the use of the cerium oxide addition appears to significantly improve the infrared reflectivity of the coating formed using the coating composition. Use of the reflective coating of the present invention in a heating device, such as a food cooking oven, will result in advantages such as faster cooking times, less energy consumption and even the need for less protective insulation.

The coating composition of the present invention upon firing produces a coating having an infrared reflectivity of at least 50% at 2.5 y-microns using a Perkin Elmer Lambda 19 UV/VIS/NIR Spectrometer with Labsphere RSA-PE 19 Reflectance Spectroscopy Accessory. A conventional porcelain enamel coating for use in food cooking applications displays an infrared reflectivity of less than about 20% The porcelain enamel composition preferably comprises from about 50% to about 95% by weight of the glass component. The glass component of the enamel

composition may comprise one or more silicate glass frits. Preferably, the glass component provides a composition as follows: Oxide Weight % Al203 0-20 BaO 0-20 B203 0-30 CaO 0-30 K2O 0-20 Li2O 0-15 Na,-O 0-20 P205 0-20 Sb2O3 0-30 SiO2 10-60 TiO2 0-30 ZnO 0-20 ZrO2 0-20 CeO2 0-5 F 0-10 The enamel composition may be utilized in connection with various metal substrates such as low carbon steel, stainless steel and aluminum. However, the present invention is especially well-suited for use on low carbon steel substrates such as those that are typically employed in the appliance business to produce food cooking ovens.

The enamel compositions according to the present invention are suitable for application to a substrate using conventional techniques such as, for example, either dry

or a wet application processes. Wet techniques such as dipping and flow coating are well-known as well as electrophoretic application which is discussed in U.S. Patent Nos. 5,002,903, 4,085,021 and 3,841,986. The disclosures of the '903, '021 and '986 patents are incorporated herein by reference for their teachings relative to the electrophoretic application of porcelain enamel coating compositions. Dry application techniques are also well-known and discussed in U.S. Patent Nos. 4,110,487 and 3,928,668. The disclosures of the '487 and '668 patents are incorporated herein by reference for their teachings relative to the dry or electrostatic application of porcelain enamel coating compositions.

Whether applied by the wet or dry process, the coating composition of the present invention may be applied directly or indirectly to the metal substrate. Indirect application would involve the primary application of a ground coat or bonding coat.

Depending upon the specific application (e.g., pickled or unpickled finished, desired reflectivity, etc.), a ground coat may be required. In general, the coating composition may be applied at a rate of 40 to 80 grams per square foot so as to provide a coating thickness of from about 5 to about 10 mils subsequent to firing.

Articles that have been coated with the coating composition of the present invention may be fired in a conventional manner using conventional firing equipment.

Firing is generally conducted at a temperature of 790"C to about 900"C for a period of about 3 to about 14 minutes.

The glass frit or frits that comprise the glass component may be prepared utilizing conventional glass melting techniques. A conventional ceramic refractory,

fused silica or platinum crucible may be used to prepare the glass frit, molten glass being formed in the crucible and then converted to glass frit using water-cooled rollers and milling equipment. It will be appreciated that the step of producing the glass frits is not per se critical and any of the various techniques well-known to those skilled in the art can be employed.

The glass frits are combined with the cerium oxide and various mill additions.

It will be appreciated that the mill additions will vary depending upon the specific application technique being employed. However, for electrophoretic applications the frits may be milled to an aqueous slip in a conventional ball mill and a typical range of mill additions, for example, is as follows: Wet Enamel Mill Addition for Dipping and/or Flow Coating Mill Addition % Bv Weight Glass Components (Frits) 80 - 100 Clays 4-7 Cerium oxide 0.5 - 3 TiO2 0 - 20 SiO2 0 - 10 Potassium Nitrate 0 - 2 Bentonite 0 - 2 Magnesium Carbonate 0 - 2 Water 45 - 49 cc/kg Fineness 2 - 3/ 200 mesh/ 50 ml.

Specific Gravity 1.70 - 1.73 Application 40 - 60 grams/square foot

Wet Electrophoretic Mill Addition Mill Additives % By Weight Glass component (Frits) 80 - 100 Opacifier (TiO2) 0 - 10 Cerium oxide 0.5 - 3 Quartz, 325 m. Quartz 0 - 10 Colloidal Silica 0.5 - 1.5 Bentonite 0.25 - 0.50 The resultant slip preferably provides a specific gravity of 1.4 - 1.7, and a fineness range of 3 to 15 ml. retained on a 325 mesh screen from a 50 ml. sample of slurry.

As is well-known in the enamel art, there is a wide range of other acceptable mill agents or components that may also be utilized in the present invention. Also, it must be appreciated that the separate and distinct addition of cerium oxide may be attained by using cerium compounds other than cerium oxide. Specifically, one may utilize any cerium bearing compound that would decompose or oxidize at enameling (firing) temperatures and form cerium oxide. Examples of such compounds include cerium carbonate, cerium boride, cerium fluoride, hydrated cerium oxide and cerium nitrate.

Final firing of the enamel on the deposited workpiece may be carried out by conventional methods and for conventional times and temperatures. For example, firing may be conducted at a temperature of from about 790"C to about 900"C for a period of from about 3 to about 14 minutes. However, it will be appreciated that

depending upon the specific application, the glass component could be modified to provide a higher or lower firing system that affords good reflectivity by virtue of the cerium oxide addition.

It will be appreciated that products coated with enamel compositions made in accordance with the present invention have good color and gloss even when applied using electrophoretic deposition techniques. The fired appearance of the final coating is smooth and uniform and substantially free of ripples or curtaining. Additionally, enamel coatings made in accordance with the present invention are color stable and resistant to chemical attack (acid resistance) and they display good resistance to the adhesion of food soils.

The following examples are intended only to illustrate the invention and should not be construed as imposing limitations upon the claims.

Example I Frit compositions A-E having the following compositions were prepared using conventional glass melting techniques.

Weight Percent Oxide A 1) C D E B203 15.61 15.61 15.84 19.54 15.98 K2O 6.80 6.85 6.93 8.56 7.00 Na2O 8.51 8.59 8.74 10.77 8.80 P205 2.29 2.29 0.00 2.85 0.00 MgO 0.49 0.45 0.47 0.56 0.00 SiO2 44.70 44.89 45.54 56.16 45.98 TiO2 20.80(1) 20.08(2) 21.23(1) 0.00 22.24(1) ZnO 0.00 0.43 0.42 0.55 0.00 ZrO2 0.80 0.80 0.82 1.00 0.00 Subtotal 100.00 99.99 99.99 99.99 100.00 F 4.00 3.07 0.00 3.84 0.00 NO2 2.50 2.53 2.56 3.16 2.58 Note: (1) Frit makers anatase, (2) Rutile Example II Porcelain enamel coating compositions were prepared using the glass frits A, B, C, D and E of Example I to provide compositions I, II, III, IV and V. In each case the components were ground in a ball mill in a conventional manner until 2 to 15 grams were retained on a 325 mesh screen from a 50 cubic centimeter sample.

% By Weight Sample Component I II Ill Frit A 100 100 Frit B 100 Frit C Frit D Frit E *P/N 5300 1 1 1 Cerium oxide concentrate Titanium Dioxide** 0 10 0 Clay 4 4 4 Potassium Nitrate 0.125 0.125 0.125 Bentonite 0.250 0.250 0.250 Water 45 45 45 (Milliliters per 100 grams of frit) *Available from MolyCorp, Inc. comprising typically 55% CeO2, 0.5-2% SrO, 5-10% CaO, 5-9% BaO, 6-10% F and 2-6% P2O5.

**Available from Kemira, Inc. comprising titanium dioxide 92-100%, aluminum hydroxide 0-8%, silica (amorphous) 0-8%.

% By Weight Sample (cont'd) Component IV V VI Frit A Frit B Frit C 100 Frit D 100 Frit E 100 *P/N 5300 1 1 1 Cerium oxide concentrate Titanium Dioxide** 0 10 0 Clay 4 4 4 Potassium Nitrate 0.125 0.125 0.125 Bentonite 0.250 0.250 0.250 Water 45 45 45 (Milliliters per 100 grams of frit) *Available from MolyCorp, Inc. comprising typically 55 % CeO2, 0.5-2 % SrO, 5-10% CaO, 5-9% BaO, 6-10% F and 2-6% P2O^.

**Available from Kemira, Inc. comprising titanium dioxide 92-100%, aluminum hydroxide 0-8%, silica (amorphous) 0-8%.

Example III The enamel compositions I, II, III, IV and V of Example II were applied on ground coated panels with a wet application of 40 to 80 grams per square foot by conventional wet spraying and dried in a convection oven at about 150 degrees Celsius.

The samples were then fired at about 870"C for 6 minutes. The samples displayed the following properties: Sample Properties Infrared Reflectivity at 2.5 u-micron (Perkin Elmer Lambda 19 W/VIS/NIR Spectrometer with Labsphere RSA-PE 19 Reflectance Spectroscopy Accessory) I 80% for Sample fired at 16000 F/ 6 minutes II 80% for Sample fired at 16000 F/ 6 minutes III 60% for Sample fired at 16000 F/ 6 minutes IV 64% for Sample fired at 16000 F/ 6 minutes V 60% for Sample fired at 16000 F/ 6 minutes V1 56% for Sample fired at 16000 F/ 6 minutes While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.