PRODUCTION

Introduction This patent application claims the benefit of priority to U.S. Patent Application

Serial No. 10/970,880, filed October 22, 2004, which is herein incorporated by reference in its entirety.

Field of the Invention This invention relates to durable, stick resistant, stain resistant, dishwasher safe, arid thermal shock resistant cookware, cutlery and other cooking utensils comprising a MAX phase and methods for their production.

Background of the Invention Cookware with a stick resistant surface is used daily by millions of households worldwide. Desirable characteristics in a stick resistant coating of cookware include good food release properties without affecting the taste of food, thermal stability at temperatures as high as 700°F, strong bonding with the substrate, environment compatibility and economic feasibility. There are several stick resistant surfaces currently in use.

For example, DuPont produces an organic surface TEFLON® with excellent food release properties. Typically, a TEFLON® coating is applied to aluminum cookware. The aluminum provides for excellent heat conductivity while the TEFLON® provides excellent food release properties. However, TEFLON®-based stick resistant surfaces are soft and easy to scratch. A metal utensil, if used against a TEFLON®-coated surface, leaves a scar. Some cleaning utensils also leave scratches. While attempts have been made to provide TEFLON®-based stick resistant surfaces with increased scratch resistance, i.e. Calphalon One, such surfaces are still susceptible to scratching. Once the TEFLON®-based stick resistant surface is scratched, the stick resistant properties of the surface deteriorate. Further, and more importantly, TEFLON® begins to be released to th.e surrounding environment and into the human body. Recently, several research groups have shown that some chemicals used in making TEFLON ^" ® represent a health hazard. In

particular, perfluorooctanoic acid (PFOA), a chemical used to make TEFLON®, has ^" been detected in people as well as animals worldwide. PFOA has been detected in river otters in Oregon, polar bears in the Canadian Arctic, and in the blood of 96 percent of children tested in 23 states (Philadelphia Inquirer, Sep. 19, 2004). According to the U.S. Environmental Protection Agency, this chemical used to produce the stick resistant coating on pots and pans is hazardous to children and women of childbearing age, according to the U.S. Environmental Protection Agency (see EPA with the extension .gov of the world wide web). Further, cooking with TEFLON® has been reported to make a person sick with a temporary flu if a stick resistant pan gets overheated (see ewg with the extension .org of the world wide web). Birds have also been reportedly killed in houses where TEFLON® coated cookware was used (see ewg with the extension .org of the world wide web).

A hard anodized aluminum cookware is produced by Calphalon. Anodizing is a process by which a layer of extremely hard, but porous, aluminum oxide is applied to the surface of aluminum. This layer protects food from bare aluminum and helps protect the surface from wear. While marketed as a stick resistant coating, in reality use of a considerable amount of cooking oil and/or fat is required for food not to stick to this cookware. Further, at microscale levels, this layer is sponge-like in structure and caαn not be placed in the dishwasher because dishwashing detergent attaches to the layer causing permanent stains and deterioration of the integrity of the layer.

Recently, to overcome the poor food release properties and the sponge-like structure, Calphalon released a new product, Calphalon One. In this product, the aluminum is anodized and the spoαge-like layer is filled with TEFLON®. However, the presence of TEFLON® in this product represents the same concerns discussed afoove. Further, this newer product is still riot dishwasher safe.

Scanpan is a Danish manufacturer specializing in durable cookware produced using different materials solutions as well as different surface coating techniques. Their cookware line consists of a combination of aluminum and titanium to provide a durable cookware. Recently they introduced a surface coating that combines the durability of ceramics and the excellent stick resistant properties of TEFLON® (Danish Patent DK989199T). However, while this surface is more scratch resistance because of the

innovative ceramic coating, the use of TEFLON® as the final layer to provide stick resistant properties is still a concern.

Published U.S. Patent Application 2003/0022027 discloses a stick resistant cook surface comprising a substrate metal selected from stainless steel, carbon steel or titanium with a layer of ceramic nitride applied to the substrate metal.

Cast iron has a natural excellent food release properties due to its chemistry and microstructure. Further, it is thermally stable and can be used with metal utensils. However, cast iron cookware is extremely heavy requiring a strong arm to handle a 12 inch cast iron skillet. Cast iron cookware also rusts easily if not kept very dry all the time. Thus, there is a need for an environmentally friendly stick resistant coating for cookware, cutlery and. other cooking utensils.

A ternary ceramic material comprising M _n+1 AX _n (n=l,2,3) wherein M is a metal selected from the groups IIIB, FVB, VB, VIB and VIII of the periodic table of elements and/or their mixture; wherein A is selected from the groups IIIA, IVA, VA and VIA of the periodic table of elements and/or their mixture, and wherein X is carbon and/or nitrogen is described in U.S. Patent 5,882,561, U.S. Patent 5,942,455 and U.S. Patent 6,461,989.

Use of this ternary ceramic material to produce slip-casted article formers suc-h as latex gloves and condoms is described in WO 03/051791. Use of this ternary ceramic material in handling molten metals is described in DE60013322D. Use of this ternary ceramic material in resistance heating elements is described in AU774202.

Summary of the Invention

An object of the present invention is to provide a stick resistant cook surface comprising a MAX phase. Another object of the present invention is to provide a stick resistant coolring utensil, said utensil comprising a MAX phase.

Another object of the present invention is to provide a stick resistant cooling utensil comprising a conventional metal cooking utensil coated at least in part with a MAX phase. Another object of the present invention is to provide a method for producing a stick resistant cooking utensil comprising a MAX phase.

Yet another object of the present invention is to provide a method for producing a stick resistant cooking utensil which comprises coating a conventional metal cooking utensil with a MAX phase.

Detailed Description of the Invention

The present invention relates to cooking utensils and methods of producing cooking utensils which are durable, stick resistant, stain resistant, dishwasher safe, and thermal shock resistant and which comprise a MAX phase.

By "MAX phase" as used herein it is meant a material comprising !M _n+! AX _n (n=l,2,3) wherein M is a metal selected from the groups UIB, IVB, VB, VIB and VIII of the periodic table of elements and/or their mixture; wherein A is selected from trie groups IIIA, IVA, VA and VIA of the periodic table of elements and/or their mixture, and wherein X is carbon and/or nitrogen.

MAX phase possesses a low friction coefficient and is thermally very stable. It is manufactured at temperatures higher than 2600 ⁰ F with Ti as more than 70% of its constituents and no organic substances being involved at any step of the process. As shown herein, its low friction coefficient makes it difficult for food to stick while its hardness makes it very difficult to be scratched using metals utensils. Further, cytotoxicity testing has shown MAX phases to be inert. By "cooking utensil" as used herein, it is meant to include any conventional tool used in food preparation wherein a stick resistant surface is desired. Examples include, but are in no way limited to, cookware such as fry pans, sauce pans, saute pans, stock pots, woks, and omelet pans, bakeware such as cookie sheets, loaf pans, casserole dishes, pie plates and cake pans, indoor and outdoor grills and griddles and other food preparation surfaces, measuring cups and mixing bowls, cutlery, spatulas, and spoons and other mixing apparatus. When used in cutlery, the nonstick characteristics of the MAX phase prevent food from sticking to the knife blade.

In one embodiment, a cooking utensil of the present invention comprises the MAX phase. Various methods for machining of a MAX phase into a cooking utensil can be used. In one embodiment, a MAX phase cooking utensil is produced by first molding a MAX phase into a desired shape, preferably by cold pressing a MAX phase powder into a desired mold, and then sintering the molded MAX phase to full density. The sintered piece

is then machined into the form of the desired cooking utensil. The surface of the cooking utensil was then polished. As shown herein a cooking utensil comprising a MAZX phase was durable, stick resistant, stain resistant, dishwasher safe, and thermal shock resistant.

In another embodiment of the present invention the cooking utensil itself is made of a conventional substrate such as, but not limited to, aluminum, copper, stainless steel, carbon steel or titanium or a combination of different metals such as, but not limited to, laminated stainless steel and aluminum or copper, and then coated with a MAX phase, hi this embodiment, the MAX phase coating may be applied to the entire cooking utensil or alternatively only to the food contacting surface. Further, as will be understood by the skill artisan upon reading this disclosure, this coating may be applied as a single component already comprising the MAX phase or as separate components, which, when combined in the coating, form a MAX phase.

Following application of the MAX phase coating, the coating is preferably polished. Applying a MAX phase in the form of a smooth coating on the food contacting surface of conventional cookware, on the blade of a knife or other form of cutlery or the surface of another cooking utensil in contact with food results in similar durable, stick resistant, stain resistant, dishwasher safe, and thermal shock resistant characteristics to those found for cooking utensils comprised of the MAX phase. The MAIX phase comprising coating can be applied by any conventional method including, but not limited to, thermal spraying, chemical vapor deposition and physical vapor deposition. Application of a MAX phase coating to a cooking utensil is expected to satisfy requirements of the Food and Drug Association for coated cooking utensils.

In the cooking utensils of the present invention, the MAX phase preferably comprises the majority of the material used to produce the cooking utensil or to coat the cooking utensil. However, as will be understood by those of skill in the art upon reading this disclosure, the combination of heat and/or the presence of oxygen in methods for production such as thermal coating of a cooking utensil, may result in changes to the chemical properties and/or crystal structure of the starting MAX phase material. Thus, in addition to the MAX phase, the coating on a cooking utensil may also comprise oxides, nitrides and carbides.

Further, in some embodiments, the cooking utensil may comprise an additional component and/or coating to enhance its performance such as, but not limited to, TEFLON® or any other coating containing Polytetrafluoroethylene, or a PTFE like

material.. Methods for adding to and/or coating the cooking utensil of the present invention with an additional component such as TEFLON® can be performed routinely in accordance with well-established procedures for production of TEFLON® containing and/or TEFLON® coated cooking utensils. Exemplary MAX phases for use in the present invention include, but are in no way limited to Ti ₃ SiC ₂ and Ti ₂ AlC.

The following nonlimiting examples are provided to further illustrate thue present invention.

EXAMPLES

Example 1: Production of molded MAX Phase cooking pan

A 6 inch cooking pan comprising the MAX phase Ti ₃ SiC ₂ was produced by cold isostatically pressing a MAX phase powder into a cylindrical mold and sintering the resulting green body to full density. The sintered piece was then machined in the form of a frying pan. The cooking surface of the pan was polished using 1200 grit paper. The pan was then heated up on the top of a stove. With no or a little bit of oil, the pan was used to burn egg, rice, applesauce, blue berries and tomato sauce.

The pan showed excellent stick resistant behavior and good food release properties. The pan was easily cleaned by washing it with clean cold water while still hot.

Soaking the pan over night in dishwasher detergent left no mark on the smooth surface of the pan. Placing the pan in the dishwasher for 4 cycles left no evidence of degradation on the smooth surface of the pan. No stains remained after cleaning and the surface looked intact. During all tests, metal utensils were used. The pan exhibited excellent scratch resistance believed to be due to the low friction coefficient MAX phases.

A 10" aluminum pan coated with the MAX phase Ti3SiC2 was also prodxiced. The

MAX phase coating exhibited excellent adhesion to the conventional cooking utensil and was resistant to scratches. Analysis of thermally sprayed MAX phase coatings wherein the starting MAX phase was Ti ₃ SiC ₂ or Ti ₂ AlC has shown the coatings to comprise the MAX phase, TiC, as

well as some oxides, with the overall oxygen content reaching up to 15%wt in some coating.

Example 2: Production of MAX Phase coated pan

The starting material for the MAX Phase coating was made up of predominantly Ti ₂ AlC with secondary phases of TiC, Ti ₃ AlC ₂ and TiAl ₃ . The material was thermally sprayed on a 11" square aluminum pan using an air cooled high velocity ox y- fuel (HVOF) system (Metco DJ with propylene fuel gas). The spraying distance was 8 inches. The primary flow rate was 44 standard cubic feet/minute (SCFM); the secondary flow rate was 43 SCFM; and the tertiary flow was 49 SCFM. The traverse speed was 92 standard feet /minute (SFPM) and the second axis index was 0.25 inches. The deposition rate was 0.0016 inches per pass. Following spraying, the surface of the sprayed p an was ground using a 10,000 rotation per minute grinder. Three grinding flap discs were used with 36, 80 and 150 Zirconia and Alumina grit (two different cases and both grit materials worked fine). Polishing was done using a polishing disc (3M equivalent to 220 grit) mounted on the same grinder.

Analysis showed that the coating contained TiC _x , Ti ₂ AlC as well as some Ti and Al oxides. Testing showed that the coating is very scratch resistant. The article was extremely easy to use. Burned eggs, tomato sauce, ketchup, berries, sugar and milk were very easy to clean and left no stains. When seasoned, the pan exhibited very good food release properties.

As will be understood by those of skill in the art upon reading this disclosure, the scope of this invention is not meant to be limited to the specific cooking utensils and methods for production via molding and/or coating exemplified herein, but rather is meant to be inclusive of any cooking utensils and means for production which can take advantage of any of the characteristics of durabilitiy, stick resistant, stain resistance, dishwasher safe, and thermal shock resistance of these MAX phase materials.