Title of Invention	"METALLIC THERMAL BARRIER COATING "
Abstract	Metal alloys having low electrical and thermal conductivity including relatively large fractions of P-Group element additions. The P-Group elements may be selected from the group including phosphorous, carbon, boron, and silicon. The resultant alloys do not exhibit significantly increased brittleness, and are applied as a coating that provides a metallic thermal barrier coating.

Full Text

Field of the Invention The invention relates to a metallic thermal barrier coating. This invention is more particularly directed at metallic alloys, and more particularly at unique metallic alloys having low electrical and thermal conductivity. In coating form, when applied, such alloys present the ability to provide thermal barrier characteristics to a selected substrate. Background of the Invention Metals and metallic alloys have metallic bonds consisting of metal ion cores surrounded by a sea of electrons. These free electrons which arise from an unfilled outer energy band allow the metal to have high electrical and thermal conductivity which makes this c lass of m aterials c onductors. D ue to the nature o f the metallic bonds, metals and metallic alloys may exhibit a characteristic range of properties such as electrical and thermal conductivity. Typical metallic materials may exhibit values of electrical resistivity that generally fall in a range of between about 1.5 to 145 10-8 Qm, with iron having an electrical resistivity of about 8.6 10-8 Qm. Typical values of thermal conductivity for metallic materials may be in a range of between about 0.2 to 4.3 watts/cm°C, with iron exhibiting a thermal conductivity of about 0.8 watts/cm°C. By contrast, ceramics are a class of materials which typically contain positive ions and negative ions resulting from electron transfer from a cation atom to an anion atom. All of the electron density in ceramics is strongly bonded resulting in a filled outer energy band. Ceramic alloys, due to the nature of their ionic bonding, will t- exhibit a different characteristic range of properties such as electrical and thermal conductivity. Because of the lack of free electrons, ceramics generally have poor electrical and thermal conductivity and are considered insulators. Thus, ceramics may be suitable for use in applications such as thermal barrier coatings while metals are not. Designing a metal alloy to exhibit ceramic like electrical and thermal conductivities is unique- The only area where this has been utilized in material science is in the design of soft magnetic materials for transformer core applications. In such applications, exit* silicon is added to iron in order to specifically reduce the electrical conductivity to minimize eddy current losses. However, iron-silicon alloys utilized for transformer cores typically contain a maximum of 2.5 at% (atomic percent) silicon because any additional silicon embrittles the alloy. Additionally, attempts to reduce electrical conductivity of iron transformer cores have not addressed reduced thermal conductivity. Summary of the Invention A metal alloy comprising an alloy metal and greater than about 4 atomic % of at least one P-group alloying element fa method form, a method of reducing the thermal and/or electrical conductivity of a metal alloy composition comprising supplying a base metal with a free electron density, supplying a P-group alloying element and combining said P-group alloying element with said base metal and decreasing the free electron density of the base metal. Description of the Preferred Embodiment Of The Invention A metallic alloy is provided which exhibits relatively low thermal conductivity and a 1ow eloctrical conductivity. T he alloy may include primary alloying metals, such as iron, nickel, cobalt, aluminum, copper, zinc, titanium, zirconium, niobium, molybdenum, tantalum, vanadium, hafinium, tungsten, manganose, and combinations thereof, and increased fractions of P-Group elemental additions in the alloy composition. P-group elements are the non-metal and semi-metal constituents of groups IDA, IVA, VA, VIA, and VIIA found in the periodic table, including but not limited to phosphorous, carbon, boron, silicon, sulfur, and nitrogen. The metallic alloy exhibiting relatively low thermal conductivity and electrical conductivity may be provided aa a coating suitable for thermal and/or electrical barrier applications on a variety of substrates. Consistent with the present invention, metallic alloys are provided that exhibit relatively low thermal and electrical conductivity. The alloys according to the present invention may include relatively high fractions of P-group elemental alloying additions in admixture with a metal The added P-group elements may include, but are not limited to, carbon, nitrogen, phosphorus, silicon, sulfur and boron. The Pgroup elements may be alloyed with the metal according to such methods as by the addition of the P-group elements to the metal in a melt state. Preferably, an alloy according to the present invention may include P-group alloying constituents. Such constituents are preferably present at a level of at least 4 at % (atomic percent) of the alloy. Desirably, the alloy consistent with the present invention may include more than one alloying component selected from P-group elements, such that the collective content of all of me P-group elements is between about 4 at % to 50 at % Consistent with the present Invention, mo alloy may include relatively large fractions of silicon in the alloy composition. For example, an iron/silicon coating alloy can be prepared according to the present invention which coating may be applied, e.g., to any given substrate. For example, it has been found mat 5.0 atomic % of silicon, and greater, may be incorporated into the alloy without any measurable loss of toughness when employed in a coating application. As alluded to above, consistent with the present invention, the metal alloy may be applied as coating using a thennal spray process. The resulting coating maybe employed to provide a thermal and/or electrical barrier coating. The coating provides thennal and/or electrical barrier properties exhibited similar to a ceramic material, however without the associated brittleness of conventional ceramic coatings. In addition to me use as a coating, the alloy of the present invention may also be processed by any know means to process a liquid melt including conventional casting (permanent mold, die, injection, sand, continuous casting, etc.) or higher cooling rate, i.e. rapid solidification, processes including melt spinning, atomization (centrifugal, gas, water, explosive), or splat quenching. One especially preferred method is to utilize atomization to produce powder in die target size range for various thermal spray coating application devices. While not limiting me invention to any particular theory, it is believed at the time of filing that by alloying metals with P-group elements, including but not limited to carbon, nitrogen, phosphorus, and silicon, covalent bonds may be formed between the electrons in the P-group alloying element and the free electrons in the base metal, which base metal, as noted, may include iron. The interaction of the free electrons in the base metal in covalent bonds with the P-group alloying elements apparently act to reduce the free electron density of the base metal, and the outer electron energy band of the base metal is progressively filled. Accordingly, by adding significant quantities of P-group elements, the free electron density of the base metal can be continually reduced and the outer electron energy band can be progressively filled. Because the relatively high thermal conductively and electrical conductivity arise from the free electrons in the unfilled outer energy bands of the metal, as me free electron density is reduced, so are the electrical conductivity and the thermal conductivity. Therefore, the present invention provides a metal alloy that behaves similar to a ceramic with respect to electrical and thermal conductivity. Experimental Observations An exemplary alloy consistent with the present invention was prepared containing a combination of several alloying elements present at a total level of 25.0 atomic % P-group alloying elements in combination with, e.g, iron. The experimental alloy was produced by combining multiple P group elements according to the following distribution: 16.0 atomic % boron, 4.0 atomic % carbon, and 5.0 atomic % silicon with 54.5 atomic % iron, 15.0 atomic % chromium, 2.0 atomic % manganese, 2.0 atomic % molybdenum, and 1.5 atomic % tungsten. The experimental alloy was prepared by mixing the alloying elements at the disclosed ratios and then melting the alloying ingredients using radio frequency induction in a ceramic crucible. The alloy was then process into a powder form by first aspirating molten alloy to initiate flow, and men supplying high pressure argon gas to the melt stream in a close coupled gas atomization nozzle. The power which was produced exhibited a Gaussian size distribution with a mean particle size of microns. The atomized powder was further air classified to yield preferred powder sized rimer in the range of 10-45 microns or 22-53 microns. These preferred size feed stock powders were men sprayed onto selected metal substrates using high velocity oxy-fuel thermal spray systems to provide a coating on the selected substrates. Reduced thermal behavior was observed for the exemplary alloy in a variety of experiments. Specifically, a small 5 gram ingot of the exemplary alloy was arcmelted on a water cooled copper hearth. It was observed mat the alloy ingots took longer time for cooling baok to room temperature, relative to other alloys which did not contain the P-group composition noted herein. More specifically, the increased time for cooling was on the order of about 20 times longer. Additionally, while conventional metals and alloys that have been healed to high temperatures cool below their red hot radiance 1evel in a few seconds, it was observed that when the exemplary alloy herein was heated to a temperature above the red hot radiance level of the alloy, the red hot radiance persisted for several minutes after removal of the heat source. Similarly, conventional metals and metallic alloys typically cool rapidly from a melt state on a conventional water cooled copper aro-melter, and can be safely handled in a matter of a few minutes. The experimental alloy prepared M described above required in excess of 30 minutes to cool from a melt state down to a safe handling temperature after being melted on a water cooled copper hearth arc-melter. Finally, when thermally sprayed the experimental alloy powder does not transfer heat sufficiently using conventional operating parameters due to its relatively low conductivity and inability to absorb heat When using high velocity oxy-fuel thermal spray system, conventional alloys can be sprayed with equivalence ratios (kerosene fuel/oxygen fuel flow rate) equal to 0.8. Because of the low thermal conductivity of the modified experimental alloys, much higher equivalence ratios, in the range of 0.9-1.2, are necessary in order to provide sufficient heating of ttie power. Additionally, when deposited via the LENS (Laser Engineered Net Shape) process, in which a high powered laser is used to melt metal powder supplied to the focus of fhe laser by a deposition head, the very thin deposit (22S um thick weld) took excessive tune before another layer can be deposited since it glows red hot for an extended time. In fhe broad context of the present invention alloy compositions of fhe following are to be noted, with fhe numbers reflecting atomic %: SHS717 Powder, with an alloy composition of Fe (52.3), Cr (19.0), Mo (2.5), W (1.7), B (16.0), C (4.0), Si (2.S) and Mn (2.0); SHS717 win, with an alloy composition of Fe (55.9), Cr (22.0), Mo (0.6), W (0.4), B (15.6), C (3.5), Si (1.2) and Mn (05). The thermal conductivity data for fhe SHS717 coatings was measured by a Laser Flash method and fhe results are given in Table 1. Note that the wire-arc conductivity is generally lower man fhe HVOF due to the higher porosity hi the wirearc coating. Note that fhe conductivity of the coatings is lower than mat of titanium which is the lowest thermal conductivity metal and at room temperature are even lower than alumina ceramic (see Table 2).(Table Removed) We claim: 1. A metallic thermal barrier alloy coating comprising iron wherein the coating comprises a base alloy metal that is present at a level of at least about 52 atomic percent in combination with at least one of chrome, molybdenum, tungsten, manganese, cobalt, nickel, copper, and combination as herein described thereof, and at least one P-group alloying element wherein the P-group alloying element is present at a level of 5 atomic % to 50 atomic %, wherein said one or more additional P-group alloying elements are selected from the group consisting of carbon, nitrogen, phosphorous, boron, and combination as herein described thereof, wherein said metallic thermal barrier coating has a thermal conductivity equal to or less than about 10 W/m-K at 400 degrees Celsius. 2. A metallic thermal barrier coating as claimed in claim 1 wherein the base alloy metal is an iron base alloy metal. 3. The coating as claimed in claim 1 wherein the base metal is with a free electron density. 4. The coating as claimed in claim 1, wherein said at least one P-group alloying element comprises 16.0 atomic % B, 4.0 atomic % C, and 5.0 atomic % Si. 5. The coating as claimed in claims 1 or 3 or 4 wherein the free electron density of the base metal is reduced from its base metal value, and wherein said free electron density is generally representative of a fully filled outer shell after combination with said P- group alloying element. 6. The coating as claimed in claims 1 or 3 or 4 wherein the base metal is selected from the group consisting of iron, nickel, cobalt, aluminum, copper, zinc, titanium, zirconium, niobium, molybdenum, tantalum, vanadium, hafnium, tungsten, manganese, and combinations thereof. 7. A metallic thermal barrier coating as claimed in any preceding claims as and used for reducing the thermal and/or electrical conductivity of a metal alloy composition.

Documents:

3568-DELNP-2005-Abstract-(08-07-2009).pdf

3568-delnp-2005-abstract.pdf

3568-delnp-2005-assignments.pdf

3568-DELNP-2005-Claims (14-10-2009).pdf

3568-DELNP-2005-Claims-(08-07-2009).pdf

3568-delnp-2005-claims.pdf

3568-DELNP-2005-Correspondence-Others (14-10-2009).pdf

3568-DELNP-2005-Correspondence-Others-(08-07-2009).pdf

3568-DELNP-2005-Correspondence-Others-(13-04-2010).pdf

3568-delnp-2005-correspondence-others.pdf

3568-DELNP-2005-Description (Complete)-(08-07-2009).pdf

3568-delnp-2005-description (complete).pdf

3568-DELNP-2005-Form-1-(08-07-2009).pdf

3568-DELNP-2005-Form-1-(13-04-2010).pdf

3568-delnp-2005-form-1.pdf

3568-delnp-2005-form-18.pdf

3568-DELNP-2005-Form-2-(08-07-2009).pdf

3568-DELNP-2005-Form-2-(13-04-2010).pdf

3568-delnp-2005-form-2.pdf

3568-delnp-2005-form-3.pdf

3568-delnp-2005-form-5.pdf

3568-delnp-2005-gpa.pdf

3568-DELNP-2005-Others-Documents-(08-07-2009).pdf

3568-DELNP-2005-PCT-237-(08-07-2009).pdf

3568-delnp-2005-pct-237.pdf

3568-DELNP-2005-PCT-304-(08-07-2009).pdf

3568-delnp-2005-pct-304.pdf

3568-DELNP-2005-Petition-138-(08-07-2009).pdf