International Patent Application Under the Patent Cooperation Treaty

For

METHODS FOR PREPARING AND REPAIRING CHEMICALLY-RESISTANT COATINGS

By

THOMAS R. ROBERTS

METHODS FOR PREPARING AND REPAIRING CHEMICALLY- RESISTANT COATINGS

Related Applications

[0001] This international application claims benefit of priority to U.S.

Provisional Patent Application No. 61/731 ,109, filed on November 29, 2012, and entitled, "Methods for Preparing and Repairing Chemically-Resistant Coatings," which is incorporated herein by reference in its entirety.

Field of Invention

[0002] This invention relates to methods for preparing and repairing chemically-resistant coatings, such as those known as porcelain enamels and vitreous enamels. This invention also relates to articles having a chemically- resistant coating.

Background of the Invention

[0003] It is known, for example from U.S. Patent No. 5,387,439, to

manufacture porcelain enamel coatings on steel substrates. The '439 patent addresses a known problem of such coatings: they generally have poor impact strength. Thus, when tools, hardware, debris, or other material forcefully contacts the coating, or the article is subject to rough handling, the coating may be damaged. If a damaged coating encounters a harsh chemical environment such as is present in a chemical manufacturing process, the underlying steel substrate could be etched, and the process would be contaminated by the etched steel. Moreover, the steel substrate ultimately would fail, and the chemical process would no longer be contained or protected from the ambient conditions outside of the steel. The '439 patent discloses coatings having improved impact strength due to the incorporation of inorganic fibrous material into the coating. [0004] Nonetheless, porcelain enamel coatings are still vulnerable to chipping, cracking, and other mechanical damage. The '439 patent teaches that a damaged coating on a process vessel can be corrected with a complete reglassing of the vessel (col. 2, II. 38-41 ), or by the use of a tantalum (metal and/or oxide) plug (col. 8, II. 14-19). As can be appreciated, reglassing of the entire vessel represents an enormous expense in both repair effort and process downtime, at least because the vessel must be disassembled from the process, typically transported to a repair site that includes a large oven or kiln, reglassed, transported back, and re-assembled into the process. Also, a tantalum patch, usually affixed over the damage site with an epoxy, may alter the chemistry of the process environment. Any repair to glass- lined equipment employing material other than glass is considered temporary.

Therefore, methods for repairing damage to a porcelain enamel coating resulting in a chemically-resistant coating are desired. Also, methods for repairing such damage that do not require a complete reglassing are also desired. Methods that can be performed in situ or with minimal disassembly are also desired. Furthermore, methods for easily preparing a chemically-resistant coating in the first place are also sought. Articles having a chemically-resistant coating, such as a chemically- resistant coating that is easily repaired, are also desired. The various embodiments of the present invention may meet one or more of those desires, thereby solving the underlying technical problems with current coating manufacturing and repair technology.

Summary of the Invention

[0005] Now, unexpectedly, applicant has found new methods to prepare and repair chemically-resistant coatings. In some embodiments, those methods involve forming a ground coat in a softened state, and then flame-spray depositing a coating material onto the softened ground coat, followed by cooling the coating slowly to relieve stress. Those methods can be used to manufacture a chemically-resistant coating in the first place, or to repair a damaged coating, whether or not the original coating was made according to the inventive method. Advantageously, some embodiments of the present invention allow the formation of a new protective chemically-resistant coating on a portion of the substrate that blends well with adjacent pre-existing coating. In further embodiments, the methods can be used to completely reglass an article such as a reactor vessel, a cover for a reactor vessel or other vessel, a baffle, a thermowell, an agitator, an agitator shaft, a pipe, a heat exchanger, a storage tank, or other process equipment as needed. Additional embodiments of the present invention include articles containing a chemically- resistant coating made according to the present invention.

[0006] Thus, some embodiments of the present invention relate to methods for preparing a chemically-resistant coating on a substrate having a ground coat thereon, comprising: heating the substrate to a first temperature thereby forming a softened ground coat; flame-spray depositing a coating material onto the softened ground coat; and cooling the substrate slowly, thereby forming the chemically- resistant coating on the substrate.

[0007] Other embodiments relate to methods of repairing a chemically- resistant coating on a substrate in need thereof, comprising: applying a composition to a damage site on the substrate, wherein the composition: (a) comprises a ground coat material in the form of particles having a particle size distribution such that at least about 5 weight percent of the particles are smaller than 44 microns and at least about 20 weight percent of the particles are larger than 150 microns, and (b) the ground coat material comprises a frit material comprising from about 48 to about 58 weight percent of silica, from about 12 to about 22 weight percent of boric oxide, from about 1 to about 9 weight percent of potassium oxide, and from about 1 to about 9 weight percent of alumina;

firing the composition to form a softened ground coat on the substrate;

flame-spray depositing a coating material onto the softened ground coat, wherein the coating material: (a) is in the form of particles having an average size ranging from about 74 to about 177 microns, and (b) comprises from about 68 to about 74 weight percent of silica, from about 0.5 to about 2.5 weight percent of alumina, from about 7 to about 15 weight percent of sodium oxide, from about 1 to about 5 weight percent of lithium oxide, and from about 2 to about 9 weight percent of zirconium oxide; and cooling the substrate slowly, thereby repairing the chemically-resistant coating on the substrate.

[0008] Further embodiments relate to methods of preparing a chemically- resistant coating on a substrate, comprising: applying a composition to the substrate, wherein the composition: (a) comprises a ground coat material in the form of particles having a particle size distribution such that at least about 5 weight percent of the particles are smaller than 44 microns and at least about 20 weight percent of the particles are larger than 150 microns, and (b) the ground coat material comprises a frit material comprising from about 48 to about 58 weight percent of silica, from about 12 to about 22 weight percent of boric oxide, from about 1 to about 9 weight percent of potassium oxide, and from about 1 to about 9 weight percent of alumina; firing the composition to form a softened ground coat on the substrate;

flame-spray depositing a coating material onto the softened ground coat, wherein the coating material: (a) is in the form of particles having an average size ranging from about 74 to about 177 microns, and (b) comprises from about 68 to about 74 weight percent of silica, from about 0.5 to about 2.5 weight percent of alumina, from about 7 to about 15 weight percent of sodium oxide, from about 1 to about 5 weight percent of lithium oxide, and from about 2 to about 9 weight percent of zirconium oxide; and cooling the substrate slowly, thereby preparing the chemically-resistant coating on the substrate.

[0009] Additional embodiments relate to articles of manufacture comprising: (a) a metal substrate; (b) a ground coat comprising silica, boric oxide, potassium oxide, and alumina; and (c) a coating in the form of splats comprising silica, alumina, sodium oxide, lithium oxide, and zirconium oxide. Such articles can be reactor vessels, covers, baffles, thermowells, agitators, agitator shafts, pipes, heat exchangers, storage tanks, and other components useful in the chemical, petrochemical, food, pharmaceutical, plastics, cosmetic, municipal water treatment, and related industries, and anywhere a chemically-resistant surface is desirable.

Detailed Description

[0010] As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various forms. The figures are not necessarily to scale, some features may be exaggerated to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention. The Substrate

[001 1] As stated above, some embodiments of the present invention provide methods for preparing or repairing a chemically-resistant coating on a substrate. Any suitable substrate can be used, such as, for example, a metal or metal alloy. In some cases, the substrate comprises steel. In one embodiment, the substrate is a cold-rolled low-carbon steel which contains less than 0.25 weight percent of carbon. Thus, as is disclosed in A.S.M.E. Specification SA285, Grade B, or SA285M-82, Grade B, this steel often contains no more than 0.22 weight percent of carbon, no more than 0.9 weight percent of manganese, no more than 0.035 weight percent of phosphorous, no more than 0.04 weight percent of sulfur, and at least about 98 weight percent of iron. In further embodiments, the substrate is a ferrous metal or alloy thereof such as those materials disclosed on pages 23-45 to 23-46 of Robert H. Perry et al.'s "Chemical Engineers' Handbook," Fifth Edition (McGraw-Hill Book Company, New York, 1973). Thus, for example, the substrate may consist essentially of Inconel Alloy 600, Inconel Alloy 610, Inconel Alloy 625, Inconel Alloy 700, Inconel Alloy 702, Inconel Alloy 705, Inconel Alloy 713, Inconel Alloy 721 , Inconel Alloy 722, Inconel Alloy X-750, and the like.

[0012] Whether the coating is being prepared or repaired on the substrate, the substrate may need to be cleaned and prepared beforehand. Any previous chemically-resistant coating can be removed, in whole or in part. For example, an area surrounding a defect or chip in the coating can be de-enameled, exposing the raw metal. The surface of the substrate often contains many imperfections, especially after it has been fabricated and is being finished or refinished. Thus, it is desired to prepare such surface by mechanical blasting to remove imperfections such as oxides, scales, pits, tool marks, etc. [0013] In one embodiment, it is possible to prepare the surface of the substrate by blasting. As is disclosed on pages 198 to 21 1 of Andrew I. Andrews' "Porcelain Enamels: The Preparation, Application, and Properties of Enamels," Second Edition (Garrard Press, Champaign, IL, 1961 ), one may prepare such surface by mechanical blasting, by compressed air blasting, and the like. One may use conventional abrasives such as sand, steel grit, alumina grit, and the like. In one embodiment, alumina grit with a particle size smaller than 40 mesh is used. Certain embodiments provide cleaning the substrate by sand blasting, grit blasting, or a combination of both. Blasting may be continued until visual inspection reveals that the surface of the substrate has a clean, uniform grey appearance, indicating that it has been cleaned sufficiently to promote adherence between the ground coat and the substrate.

The Ground Coat

[0014] The ground coat can be any suitable material. As is known in the art, a ground coat in certain embodiments can be an alkali borosilicate glass composition which is used to develop high adherence between the substrate and subsequent coatings on the substrate. In still further embodiments, a ground coat can contain from about 10 to about 20 weight percent of boric oxide, from about 40 to about 60 weight percent of silica, and from about 15 to about 25 weight percent of alkali metal oxide(s) selected from the group consisting of the oxides of lithium, sodium, potassium, rubidium, cesium, francium, and mixtures thereof.

[0015] In one embodiment, ground coat comprises from about 60 to about 65 weight percent of silica. In another embodiment, the ground coat comprises from about 10 to about 22 weight percent of boric oxide. A further embodiment provides a ground coat comprising from about 1 to about 9 weight percent of potassium oxide. An additional embodiment includes a ground coat comprising from about 1 to about 9 weight percent of alumina. Still other embodiments include a ground coat comprising calcium oxide, cobalt oxide, nickel oxide, manganese oxide, one or more alkali metal oxides such as lithium oxide, sodium oxide, rubidium oxide, cesium oxide, francium oxide, or a combination thereof.

[0016] A ground coat composition can be prepared in any suitable manner. For example, a mixer can be used. Optionally, a suitable mixer can also comminute, that is, pulverize, or further reduce the particle size of the composition. Or a separate pulverizer can be employed. Thus, in one embodiment, a suitable mixer is a tumbling mill such as, e.g., a tube mill, a compartment mill, a rod mill, a pebble mill, a ball mill, and the like. See, e.g., pages 8-25 to 8-28 of Robert H. Perry et al.'s "Chemical Engineers' Handbook," Fifth Edition (McGraw-Hill Book Company, New York, 1973).

[0017] A ground coat composition, which is applied to the substrate and then fired to form a softened ground coat, can take the form of a slurry. In some embodiments, a sufficient amount of liquid is added to the mixer with the solid material so that a slurry containing from about 60 to about 70 weight percent of solid material is formed. That is, the slurry comprises from about 30 to about 40 weight percent liquid. The liquid can include any suitable liquid such as water, lower alcohols such as methanol, ethanol, propanol, or butanol, or combinations of any of the foregoing. Milling of this slurry in a mixer, in certain embodiments, is continued until a substantially homogeneous mixture with a particle size distribution such that at least five weight percent of the particles in the slurry are smaller than 44 microns and at least about 20 weight percent of the particles in the slurry are larger than 150 microns is produced, in some embodiments. Samples may be periodically removed from the mixer and subjected to particle size analysis to determine whether the slurry has the desired particle size distribution. See, for example, U.S. Pat. No. 4,282,006 for a discussion of the measurement of particle size distribution.

[0018] In some cases, a ground coat material can be prepared, for example, by charging into a mixer a glass batch containing from about 48 to about 58 weight percent (by total weight of the glass batch, dry basis) of silica, from about 12 to about 22 weight percent of boric oxide, from about 9 to about 19 weight percent of sodium oxide, from about 1 to about 9 weight percent of potassium oxide, and from about 1 to about 9 weight percent of alumina. In addition, this glass batch also may contain from about 1 to about 6 weight percent of calcium fluoride, from about 0.2 to about 6 weight percent of cobalt oxide, from about 0.2 to about 4 weight percent of nickel oxide, and from about 0.2 to about 3 weight percent of manganese oxide.

Optionally, one may also add various suspending agents, electrolytes, and other materials and fluids to the mixer; see, e.g., pages 360-365 of the aforementioned Andrews text.

[0019] A ground coat composition may be applied to the substrate via any suitable method, such as, for example, dipping, slushing, spraying, and combinations thereof. Any conventional spraying means may be used; see, e.g., pages 394 to 403 of the aforementioned Andrews reference. It is possible to apply the ground coat composition to the prepared substrate in such a manner that one obtains a uniform thickness after firing of from about 0.25 millimeters to about 0.5 millimeters. To achieve this goal, in general a wet film of from about 0.3 to about 0.75 millimeters can be applied to the substrate. [0020] Once the ground coat composition is applied to the substrate, the composition may be dried if it is in the form of a slurry. Any suitable drying method can be used, including air drying, heated drying, forced air drying, force drying in an oven, and combinations thereof. Moisture content of a dried ground coat

composition, in some cases, is less than about 10 weight percent, or less than about 1 weight percent in other cases. Then the ground coat composition is fired at any suitable temperature. Firing the ground coat composition can employ any suitable method, such as, for example, induction heating, placing the workpiece in an oven or kiln, or combinations thereof. Induction heating, comprising placing one or more induction coils in proximity to the substrate, can be employed in certain embodiments of the present invention. The induction coil heats the metal substrate, which in turn heats the ground coat composition. The ground coat composition is heated to a temperature at which it vitrifies. Some embodiments provide the ground coat so formed is heated to or held at a temperature at which the ground coat is softened. Such a temperature can be above the ground coat's glass transition temperature, in certain embodiments. Other embodiments provide a softened ground coat at a temperature at which the ground coat does not significantly flow or deform on the time scale of the manufacturing operation that applies the coating material.

[0021] In some embodiments, the optionally-dried ground coat composition on the substrate is subjected to a temperature ranging from about 810 to about 910 degrees Centigrade for a time ranging from about 20 to about 150 minutes. It is possible to subject the dried substrate to a temperature ranging from about 850 to about 880 degrees Centigrade for a time ranging from about 20 to about 150 minutes, in certain embodiments. Still other embodiments provide firing the ground coat composition at a temperature ranging from about 1 ,500 to about 1 ,600 degrees Fahrenheit (about 816 to about 871 degrees Centigrade).

The Coating Material

[0022] The coating material that is deposited onto the softened ground coat to form the chemically-resistant coating can be any suitable material. In some embodiments, the coating material comprises silica, alumina, sodium oxide, lithium oxide, and zirconium oxide. In other embodiments, the coating material comprises from about 68 to about 74 weight percent of silica. Further embodiments provide a coating material comprising from about 0.5 to about 2.5 weight percent of alumina. Additional embodiments include a coating material comprising from about 7 to about 15 weight percent of sodium oxide. Yet other embodiments include a coating material comprising from about 1 to about 5 weight percent of lithium oxide. Still further embodiments provide a coating material comprising from about 2 to about 9 weight percent of zirconium oxide. In one embodiment, the frit contains from about 70 to about 72 weight percent of silica, from about 1 to about 2 weight percent of alumina, from about 1 1 to about 14 weight percent of sodium oxide, from about 1 to about 3 weight percent of lithium oxide, and from about 2 to about 6 weight percent of zirconium oxide.

[0023] The coating material can also contain suspending agents such as montmorillonitic type clays, for example. Some embodiments provide from about 0.1 to about 0.6 weight percent of such suspending agent(s), by weight of solid material. Any conventional electrolyte (such as potassium chloride, barium chloride, aluminum chloride, calcium chloride, and the like) may be used, in additional embodiments, in any suitable amount. In some cases, from about 0.02 to about 0.6 weight percent of such electrolyte (by weight of dry solid material) may be used.

[0024] The coating material can be prepared in any suitable manner. As explained for the ground coat, the raw ingredients for the coating material can be introduced into a mixer that also comminutes, in some embodiments. Once mixed, the ingredients can be vitrified into a frit, quenched, dried, and then reduced to particles again. In preparation for flame-spray deposition, a particle size of 80 - 200 mesh can be used in certain embodiments. In other embodiments, a mesh size of 100 - 200 is used. In still other embodiments, a mesh size of 80 - 100 is employed. As is known in the art, 80 mesh corresponds to a particle size of about 177 microns, 100 mesh corresponds to a particle size of about 149 microns, and 200 mesh corresponds to a particle size of about 74 microns. In still other embodiments, the coating material is in the form of particles having an average size ranging from about 1 15 to about 125 microns.

Forming the Chemically-Resistant Coating

[0025] The substrate and the workpiece can be heated by any suitable method for any purpose requiring heat. In addition, each of heating the substrate, firing, optionally maintaining the temperature of the softened ground coat by heating, and cooling the substrate slowly, can be accomplished by the same or different heating methods. The ground coat in one embodiment can be formed in a kiln or oven. A heat gun can maintain the temperature of the softened ground coat, if necessary, before and during flame-spray deposition. Then an induction coil can be used to apply induction heating to the substrate to allow the substrate to cool slowly, thereby allowing the coating material and the ground coat to relieve any stresses. [0026] Applicant has found that certain embodiments of the present invention afford a previously unavailable degree of freedom. Because of the ease of employing those embodiments, and the robust nature of the resulting chemically- resistant coatings, repairs of damaged coatings in the field are now possible. Some embodiments employ induction heating as the sole or primary heat source. In certain cases, induction heating obviates the need to disassemble, transport, and deglass process equipment that has a damaged porcelain enamel coating. Thus, in one embodiment, heating the substrate comprises applying induction heating. In a further embodiment, providing a softened ground coat comprises applying induction heating. In another embodiment, cooling the substrate slowly comprises applying induction heating.

[0027] Flame-spray deposition of the coating material can occur according to any suitable method. Commercially-available flame spray equipment can be used in some embodiments. The coating material is loaded in the flame sprayer, and then deposited onto the softened ground coat. Optionally, the temperature of the softened ground coat is maintained by heating, such as for example, by applying induction heating to the substrate. In another embodiment, the flame-spray deposition occurs rapidly after firing of the ground coat under circumstances that allow the ground coat to maintain a softened state throughout the flame-spray deposition. In some cases, the ground coat is maintained at a temperature greater than about 1450 degrees Fahrenheit (about 788 degrees Centigrade) during flame- spray depositing. In other cases, the ground coat is maintained at a temperature greater than about 1480 degrees Fahrenheit (about 804 degrees Centigrade) during flame-spray depositing. Some embodiments provide a different process in lieu of or in addition to flame-spray depositing known as hot dusting. In such embodiments, the coating material in particulate form is heated and dusted on the softened ground coat. Then the substrate is cooled slowly, as described elsewhere herein. Accordingly, some embodiments relate to methods for preparing or repairing a chemically-resistant coating on a substrate having a ground coat thereon, comprising: heating the substrate to a first temperature thereby forming a softened ground coat; hot-dust depositing a coating material onto the softened ground coat; and cooling the substrate slowly, thereby preparing or repairing the chemically-resistant coating on the substrate.

[0028] Flame-spray depositing the coating material onto the softened ground coat will cause the coating material to form a layer of "splats" in some embodiments. Upon microscopic inspection of a cross-section of certain chemically-resistant coatings of the present invention, those splats will appear as flattened or deformed spheres characteristic of flame-spray deposition. In some embodiments, the splats have an average volume ranging from about 2.1 x 10 ^"13 m ³ to about 2.9 x 10 ^"12 m ³ . In other embodiments, the splats have an average volume ranging from about 2.1 x 10 ^"13 m ³ to about 1 .7 x 10 ^"12 m ³ . In still other embodiments, the splats have an average volume ranging from about 7.9 x 10 ^"13 m ³ to about 1 .0 x 10 ^"12 m ³ .

[0029] Some embodiments therefore provide a coating material in the form of splats, wherein the splats comprise from about 68 to about 74 weight percent of silica. Other embodiments include splats comprising from about 0.5 to about 2.5 weight percent of alumina. Further embodiments involve splats comprising from about 7 to about 15 weight percent of sodium oxide. Still other embodiments include a coating in the form of splats that comprise from about 1 to about 5 weight percent of lithium oxide. Additional embodiments of the present invention contain splats that comprise from about 2 to about 9 weight percent of zirconium oxide.

[0030] The thickness of the layer of coating material can be any suitable dimension. In some embodiments, the thickness of the coating material ranges from about 0.5 to about 1 .0 millimeter.

[0031] Another aspect of the invention relates to the relief of stress in the chemically-resistant coating. Such stress can appear in the ground coat, in the flame-spray deposited coating material, another layer of material the skilled artisan has chosen to employ with the foregoing materials, or a combination thereof. Such stress can be relieved, for example, by holding the workpiece or a portion thereof where the chemically-resistant coating is being formed at an elevated temperature. In some cases, that elevated temperature is at or above the glass transition temperature of the ground coat. In other cases, that elevated temperature is at or above the glass transition temperature of the flame-spray deposited coating material. In still other cases, that elevated temperature is at or above the glass transition temperature of both the ground coat and the flame-spray deposited coating material. Sometimes, the skilled artisan may prefer to use the annealing temperature range of one or more materials as a reference point. Accordingly, in some cases, that elevated temperature is at or above the annealing temperature range of the ground coat. In other cases, that elevated temperature is at or above the annealing temperature range of the flame-spray deposited coating material. In still other cases, that elevated temperature is at or above the annealing temperature ranges of both the ground coat and the flame-spray deposited coating material.

[0032] The time it takes to cool the substrate slowly may depend on one or more factors, such as, for example, the size of the workpiece or the portion of the workpiece having new or repaired chemically-resistant coating, the mass and thickness of the coating, the geometry of the workpiece (substantially planar, concave, convex, or complex), and the physical properties of the substrate, ground coat, and coating material (glass transition temperature, coefficient of thermal expansion). In some embodiments, therefore, cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the ground coat in a time period of not less than thirty minutes after the flame-spray depositing. Other embodiments allow the substrate to pass through the glass transition temperature of the coating material in a time period of not less than thirty minutes, not less than one hour, or not less than two hours after the flame-spray depositing.

[0033] Some embodiments of the present invention provide additional layers. For example, more than one ground coat can be applied before the flame-spray deposition. One or more intermediate coats can be included as well. More than one layer of flame-spray deposited coating materials also appear in certain

embodiments. Such additional layers can comprise any suitable materials and exhibit any suitable characteristics. For example, in a few embodiments, the various layers of material have coefficients of thermal expansion such that each layer has a coefficient numerically between the adjacent materials, so that the overall coating performs adequately upon heating and cooling. It is desirable in further

embodiments that the flame-spray deposition occurs onto a layer of material that is in a softened state. Testing the Chemically-Resistant Coating

[0034] Chemically-resistant coatings of the present invention can be characterized and distinguished from other coatings in numerous ways. To determine the identity and relative amount of the ingredients in a coating, any suitable method can be used. It is possible, in some circumstances, to employ energy-dispersive X-ray spectroscopy ("EDX"), X-ray fluorescence ("XRF"), various forms of electron microscopy, petrography, optical microscopy, and other analytical techniques to determine the identity and amount of components of a coating. In addition, it is possible to calculate the composition of a coating from the relative amounts of raw ingredients used to make the ground coat material, the frit, if any, of the ground coat material, the mill additions, if any, of the ground coat material, the frit, if any, of the coating material, the mill additions, if any, of the coating material, and any other ingredients. Two methods of such calculations may be mentioned, and both are fully explained in Chapter 6, Enamel Calculations, of the Andrews text. The first is the so-called "Factor Method," because it employs numerical factors for estimating the amount of material formed from a given raw material. For example, it is estimated that 1 gram of soda ash (Na ₂ C0 ₃ ) will yield 0.585 grams of sodium oxide (Na ₂ 0) after firing, so the factor used to calculate the relative amount of sodium oxide in the final coating from the amount of soda ash added is 0.585. See Andrews, Table 23, page 218. The second is the so-called "Chemical Method," which relies on sorting the resulting oxides into basic oxides having the formula R ₂ 0 or RO, intermediate oxides having the formula R2O3, and acidic oxides having the formula R0 ₂ . See Andrews, page 230. Those methods are known to those having ordinary skill in the art, so are not further elucidated here. [0035] The coefficients of thermal expansion of the substrate, ground coat, and coating material can be any suitable values. For example, in one embodiment, the chemically-resistant coating has a coefficient of thermal expansion ranging from about 85 to about 89 X 10 ^"7 centimeters per centimeter per degree centigrade. In this embodiment, the substrate to be coated may be, e.g., a concave surface such as, e.g., the inside of a reactor vessel. In another embodiment, the chemically-resistant coating has a coefficient of thermal expansion ranging from about 100 to about 105 X 10 ^"7 centimeters per centimeter per degree centigrade. In this embodiment, the substrate to be coated may be a convex surface such as, e.g., the blade of an agitator. In still other embodiments, the substrate comprises low carbon steel, and has a coefficient of thermal expansion of about 125 X 10 ^"7 centimeters per centimeter per degree centigrade. An additional embodiment provides a ground coat having a coefficient of thermal expansion of about 100 X 10 ^"7 centimeters per centimeter per degree centigrade. Still another embodiment provides a coating material having a coefficient of thermal expansion of about 80 X 10 ^"7 centimeters per centimeter per degree centigrade.

[0036] The glass transition temperature of the coating, or of the ground coat, coating material, or any component thereof, can be measured using differential scanning calorimetry and thermal dilatometry, as is known in the art.

[0037] The acid resistance of the coated substrate may be tested in substantial accordance with the test described in U.S. Pat. No. 4,407,868. The standard test JIS R-4301 discussed in EXAMPLE 6 of such patent is substantially the same test as described in DIN 2743. The afore-mentioned Andrews text describes on page 586 the acid resistance test known as ASTM Desig. C 283-54 (1954). Such a test is also acceptable, as are any other suitable tests. [0038] When the testing of the coated substrate is done in accordance with DIN 2743 and the substrate is exposed to a vapor of 20 volume percent of hydrochloric acid, the chemically-resistant coating may lose no more than about 0.3 grams per square meter per day, in some embodiments of the present invention.

[0039] The thermal shock properties of the chemically-resistant coating may be tested in accordance with A.S.T.M. Standard Test C385-58. An impact resistance test may be conducted with the apparatus illustrated in FIG. 3 of the '439 patent. An electrical test apparatus also may be utilized. The electrical test apparatus can be a 20,000 volt alternating current test spark tester supplied by the DeDietrich Co. of Corpus Christi, Tex. Using such an apparatus, a chemically- resistant coating of the present invention can be subject to a 20 KV spark test to test the integrity of the coating. Different areas of the coating can be tested to measure the overall quality of the coating.

Examples

[0040] The following examples are presented to illustrate the claimed invention but are not to be deemed limitative thereof. Unless otherwise specified, all parts are by weight and all temperatures are in degrees Centigrade. The equipment, materials, volumes, weights, temperatures, sources of materials, manufacturers of equipment, and other parameters are offered to illustrate, but not to limit, the invention. All such parameters can be modified within the scope of the claimed invention.

Example 1 - Ground Coat on a Steel Substrate [0041] To a tumbling mill (such as those manufactured by the Curtis

Manufacturing Company or U.S. Stoneware of East Palestine, OH) is charged 36.34 parts of feldspar (sold by the Pacer Corporation of Custer, SD, as "Custer Feldspar"), 23.65 parts of dehydrated borax (sold by the U.S. Borax Corporation of Death Valley, Calif, as "anhydrous borax"), 2.16 parts of fluorspar (sold by READE Advanced Materials of East Providence, Rl as " fluorspar powder"), 2.03 parts of potassium nitrate (sold by the Interstate Chemical Company of West Middlesex, Pa. as "potash niter"), 9.02 parts of sodium carbonate (sold by the Interstate Chemical Company as "soda ash"), 25.1 1 parts of quartz (sold by Short Mountain Silica of Mooresburg, TN as "glass sand"), 0.85 parts of cobalt oxide (sold by Atlantic Equipment Engineers of Bergenfield, NJ as "black cobalt oxide powder," Item # CO-601 ), 0.47 parts of nickel oxide (sold by Atlantic Equipment Engineers as "green nickel oxide powder," Item # NI-601 ), and 0.38 parts of manganese oxide (sold by Atlantic Equipment Engineers as "manganese dioxide powder," Item # MN-601 ). Thereafter, these reagents are mixed by tumbling them for two hours at a speed of 30 revolutions per minute.

[0042] The mixture thus produced is then charged to a 5200 mL cylindrical crucible comprised of 92 per cent alumina; this crucible can be obtained from

Antaeus Hi-Tech, Zhengzhou City, Henan Province, China. The crucible containing the glass batch is then charged to a Harper Furnace, model number

H4S121412EKA30S (manufactured by the Harper Electric Furnace Corporation of Lancaster, N.Y.); both the crucible and the furnace are preheated to a temperature of 1 ,400 degrees Centigrade (2,552 degrees Fahrenheit) prior to the time the batch was charged to the crucible or placed into the furnace.

[0043] The glass batch is heated at 1 ,400 degrees Centigrade for 4.0 hours. At the end of this time, a fiber is pulled from the glass batch to check that the material is fully smelted and in solution. Thereafter, the material is poured from the crucible into a thirty-gallon quenching kettle at a temperature of 55 degrees

Fahrenheit (12.8 degrees Centigrade) which is filled with 25 gallons of water, thereby quenching the molten glass.

[0044] Water is removed from the kettle, and the quenched frit is then dried in the kettle to a moisture content of less than 1 .0 weight percent.

[0045] To a number 2 jar mill (manufactured by U.S. Stoneware Corporation) is charged 100 parts of the dried frit, 7 parts of OM4 ball clay (sold by Great Lakes Clay of Elgin, IL), 40 parts of number 3 glass sand, 0.155 parts of sodium nitrite (sold by the Interstate Chemical Corporation as sodium nitrite), 0.155 parts of anhydrous borax, and 44 parts of deionized water. The total weight of the charge to the jar mill, dry basis, is 3,234 grams; the grinding media used is 6,600 grams of 1 .25 inch high- density alumina balls and 3,300 grams of 1 .0 inch high-density alumina balls. The mixture is then milled at a rate of 34 revolutions per minute for two hours.

[0046] The slurry thus produced is checked for particle size distribution by passing it through a series of 100 mesh Tyler and 325 mesh Tyler steel sieves;

milling is continued until 20 weight percent of the particles in the slurry are retained on the 100 mesh sieve, and 75 percent of the particles are retained on the 325 mesh sieve.

[0047] Deionized water is added to the slurry until its specific gravity was 1 .78. Thereafter, the slurry is placed into a DeVilbiss JGV560 Spray Gun (manufactured by the DeVilbiss Company of Toledo, Ohio).

[0048] A 6" X 6" X 0.5" thick steel plate (SA285, Grade B steel, such as is available from the Nucor Corporation of Charlotte, NC) is used as the substrate for the ground coat composition. Before deposition, the plate is grit blasted with minus 40 mesh alumina at 80 pounds per square inch until a clean sample is obtained. Thereafter, the clean sample is sprayed with the ground coat slurry material until a wet film with a wet film thickness of 0.62 millimeters is obtained. The coated substrate is then allowed to air dry under ambient conditions for 2.0 hours.

[0049] The dried plate is then charged to Cooley BL4 Electric Furnace which is preheated to a temperature of 870 degrees Centigrade. The plate is subjected to this temperature for a period of 40 minutes.

Example 2 - Preparing Coating Material

[0050] The coating material is prepared as follows. To the aforementioned tumbling mill is charged 9.09 parts of the aforementioned feldspar, 1 .52 parts of calcium carbonate (sold by Interstate Chemical Company), 3.57 parts of magnesium carbonate (sold by American Elements of Los Angeles, CA, as magnesium carbonate), 4.24 parts of potassium nitrite (sold by Interstate Chemical Company as potassium nitrite), 5.00 of sodium nitrate (sold by American Elements as sodium nitrate), 16.79 parts of the aforementioned sodium carbonate, 5.9 parts of zirconium silicate (sold by the Tarn Ceramic Products Corporation of Niagara Falls, N.Y. as "Zircosil"), 2.17 parts of the aforementioned anhydrous borax, 4.2 parts of lithium carbonate (sold by American Elements as lithium carbonate), 62.18 parts of the aforementioned quartz, 1 .0 parts of the aforementioned cobalt oxide, and 1 .2 parts of black iron oxide (sold by Atlantic Equipment Engineers as "black iron oxide

(magnetite)," Item # FE-602). The mixture is then mixed for 2.0 hours at a speed of 30 revolutions per minute.

[0051] The mixture thus produced is charged to a crucible comprised of 92 per cent alumina; this crucible can be obtained from Antaeus Hi-Tech, Zhengzhou City, Henan Province, China. The crucible containing the glass batch is then charged to a Harper Furnace, model number H4S121412EKA30S (manufactured by the Harper Electric Furnace Corporation of Lancaster, N.Y.); both the crucible and the furnace are preheated to a temperature of 1 ,400 degrees Centigrade prior to the time the batch is charged to the crucible or placed into the furnace.

[0052] The glass batch is heated at 1 ,400 degrees Centigrade for 4.0 hours. At the end of this time, a fiber is pulled from the glass batch to check that the material is fully smelted and in solution. Thereafter, the material is poured from the crucible into a thirty-gallon quenching kettle at a temperature of 55 degrees

Fahrenheit which is filled with 25 gallons of water, thereby quenching the molten glass. Water is removed from the kettle, and the quenched frit is then dried in the kettle to a moisture content of less than 1 .0 weight percent.

[0053] To a number 2 jar mill (manufactured by U.S. Stoneware Corporation) is charged 100 parts of the dried frit, 0.62 parts of purified Wyoming bentonite (sold by Wyo-Ben, Inc., of Billings, MT), 0.62 parts of potassium chloride (sold by

Interstate Chemical Company as potassium chloride), and 35 parts of deionized water. The total weight of the charge to the jar mill, dry basis, is 2,334.8 grams; the grinding media used is 6,600 grams of 1 .25 inch high-density alumina balls and 3,300 grams of 1 .0 inch high-density alumina balls. The mixture is then milled at a rate of 34 revolutions per minute for two hours.

[0054] The mixture thus produced is charged to a crucible comprised of 90 percent alumina as described above; this crucible is then charged to the Harper Furnace. Both the crucible and the furnace are preheated to a temperature of 1 ,400 degrees Centigrade prior to the time the batch is charged to the crucible or placed into the furnace. [0055] The mixture is heated at 1 ,400 degrees Centigrade for 4.0 hours. At the end of this time, a fiber is pulled to check that the material is fully smelted and in solution. Thereafter, the now-formed coating material is poured from the crucible into a thirty-gallon quenching kettle at a temperature of 55 degrees Fahrenheit which is filled with 25 gallons of water, thereby quenching the molten coating material. Water is removed from the kettle, and the quenched coating material is then dried in the kettle to a moisture content of less than 1 .0 weight percent.

[0056] The coating material thus produced is returned to the jar mill and milled until an appropriate particle size distribution results. The coating material is checked for particle size distribution by passing it through a series of 100 mesh Tyler and 325 mesh Tyler steel sieves; milling continues until 10 weight percent of the particles are retained on the 100 mesh sieve, and 80 percent of the particles are retained on the 325 mesh sieve. Alternatively, particles having a size distribution ranging from about 1 15 microns to about 125 microns can be chosen through selective use of appropriate sieves.

Example 3 - Coating Material Flame-Spray Deposited onto the Heated, Softened Ground Coat

[0057] The coating material particles are loaded into a flame sprayer, and flame- spray deposited on the substrate. The aforementioned, ground-coated 6" X 6" X 0.5" thick steel plate with the ground coat thereon was used as the target. The steel plate is coated immediately upon removal from the electric furnace. Optionally, an induction coil also maintains the substrate at about 1450 to about 1480 degrees Fahrenheit (about 788 to about 804 degrees Centigrade). A suitable temperature detection device, such as a thermocouple or an infrared laser temperature detector, may monitor the temperature. The flame sprayer deposits the coating material onto the softened ground coat. Additional layers of various alike or different compositions can be added, optionally while the ground coat remains in a softened state.

[0058] Then the substrate is allowed to cool slowly by the application of an induction coil to heat the substrate. After two hours, the substrate cools below the glass transition temperature of the coating material. The substrate is then allowed to cool to room temperature at a rate of about 120 degrees Fahrenheit (about 67 degrees Centigrade) per hour.

Example 4 - Testing the Chemically-Resistant Coating

[0059] The coated steel plate from Example 3 is checked for electrical conductivity using the 20,000 volt test procedure; the plate should be an effective insulator.

[0060] The coating thickness is measured by a Fisher Deltascope thickness meter, and the mean thickness likely ranges from about 1 .28 to about 1 .52 millimeters; 32 readings are taken.

[0061] The sample is tested in accordance with the impact resistance test described in the specification of the '439 patent. Following each impact, the sample is tested by the aforementioned Electric Spark Test, using 20,000 volts.

Example 5 - Convex Substrate

[0062] In substantial accordance with the procedure of Examples 1 -3, a coated substrate is prepared, with the exceptions that (1 ) the target used is a convex-shaped steel substrate (SA-285), (2) the coating material is made from a glass batch which comprised 2.3 parts of potassium oxide, 15.3 parts of sodium oxide, 4.0 parts of barium oxide, 1 .0 parts of calcium oxide, 1 .3 parts of zinc oxide, 2.6 parts of lithium oxide, 69.8 parts of silica, and 3.7 parts of alumina. The coated and fired substrate should have properties comparable to the coated substrate of Example 3.

Various Embodiments

[0063] Embodiment 1 . A method for preparing a chemically-resistant coating on a substrate having a ground coat thereon, comprising:

heating the substrate to a first temperature thereby forming a softened ground coat; flame-spray depositing a coating material onto the softened ground coat; and cooling the substrate slowly, thereby forming the chemically-resistant coating on the substrate.

[0064] Embodiment 2. The method of embodiment 1 , wherein the substrate comprises steel.

[0065] Embodiment 3. The method of any one of embodiments 1 -2, wherein the ground coat comprises from about 60 to about 65 weight percent of silica.

[0066] Embodiment 4. The method of any one of embodiments 1 -3, wherein the ground coat comprises from about 10 to about 22 weight percent of boric oxide.

[0067] Embodiment 5. The method of any one of embodiments 1 -4, wherein the ground coat comprises from about 1 to about 9 weight percent of potassium oxide. [0068] Embodiment 6. The method of any one of embodiments 1 -5, wherein the ground coat comprises from about 1 to about 9 weight percent of alumina.

[0069] Embodiment 7. The method of any one of embodiments 1 -6, wherein the ground coat comprises calcium oxide, cobalt oxide, nickel oxide, manganese oxide, one or more alkali metal oxides, or a combination thereof.

[0070] Embodiment s. The method of any one of embodiments 1 , 2, or 7, wherein the coating material comprises from about 68 to about 74 weight percent of silica, from about 0.5 to about 2.5 weight percent of alumina, from about 7 to about 15 weight percent of sodium oxide, from about 1 to about 5 weight percent of lithium oxide, and from about 2 to about 9 weight percent of zirconium oxide.

[0071] Embodiment 9. The method of any one of embodiments 1 , 2, or 7, wherein the coating material comprises from about 68 to about 74 weight percent of silica.

[0072] Embodiment 10. The method of any one of embodiments 1 , 2, 7, or 9, wherein the coating material comprises from about 0.5 to about 2.5 weight percent of alumina.

[0073] Embodiment 1 1 . The method of any one of embodiments 1 , 2, 7, 9, or 10, wherein the coating material comprises from about 7 to about 15 weight percent of sodium oxide. [0074] Embodiment 12. The method of any one of embodiments 1 , 2, 7, 9-1 1 , wherein the coating material comprises from about 1 to about 5 weight percent of lithium oxide.

[0075] Embodiment 13. The method of any one of embodiments 1 , 2, 7, 9-12, wherein the coating material comprises from about 2 to about 9 weight percent of zirconium oxide.

[0076] Embodiment 14. The method of any one of embodiments 1 -13, wherein heating the substrate comprises applying induction heating.

[0077] Embodiment 15. The method of any one of embodiments 1 -14, wherein cooling the substrate slowly comprises applying induction heating.

[0078] Embodiment 16. The method of any one of embodiments 1 -15, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the ground coat in a time period of not less than thirty minutes after the flame-spray depositing.

[0079] Embodiment 17. The method of any one of embodiments 1 -16, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than thirty minutes after the flame-spray depositing. [0080] Embodiment 18. The method of any one of embodiments 1 -17, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than one hour after the flame-spray depositing.

[0081] Embodiment 19. The method of any one of embodiments 1 -18, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than two hours after the flame-spray depositing.

[0082] Embodiment 20. A method of repairing a chemically-resistant coating on a substrate in need thereof, comprising:

applying a composition to a damage site on the substrate, wherein the composition:

(a) comprises a ground coat material in the form of particles having a particle size distribution such that at least about 5 weight percent of the particles are smaller than 44 microns and at least about 20 weight percent of the particles are larger than 150 microns, and

(b) the ground coat material comprises a frit material comprising from about 48 to about 58 weight percent of silica, from about 12 to about 22 weight percent of boric oxide, from about 1 to about 9 weight percent of potassium oxide, and from about 1 to about 9 weight percent of alumina;

firing the composition to form a softened ground coat on the substrate;

flame-spray depositing a coating material onto the softened ground coat, wherein the coating material: (a) is in the form of particles having an average size ranging from about 74 to about 177 microns, and

(b) comprises from about 68 to about 74 weight percent of silica, from about 0.5 to about 2.5 weight percent of alumina, from about 7 to about 15 weight percent of sodium oxide, from about 1 to about 5 weight percent of lithium oxide, and from about 2 to about 9 weight percent of zirconium oxide; and

cooling the substrate slowly, thereby repairing the chemically-resistant coating on the substrate.

[0083] Embodiment 21 . The method of embodiment 20, wherein the firing comprises applying induction heating.

[0084] Embodiment 22. The method of any one of embodiments 20-21 , wherein the cooling the substrate slowly comprises applying induction heating.

[0085] Embodiment 23. The method of any one of embodiments 20-22, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than thirty minutes after the flame-spray depositing.

[0086] Embodiment 24. The method of any one of embodiments 20-23, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than one hour after the flame-spray depositing. [0087] Embodiment 25. The method of any one of embodiments 20-24, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than two hours after the flame-spray depositing.

[0088] Embodiment 26. The method of any one of embodiments 20-25, wherein the composition is in the form of a slurry and comprises from about 30 to about 40 weight percent liquid.

[0089] Embodiment 27. The method of embodiment 26, wherein the liquid comprises water.

[0090] Embodiment 28. The method of any one of embodiments 20-27, further comprising drying the composition before the firing.

[0091] Embodiment 29. The method of any one of embodiments 20-28, wherein the coating material in the form of particles has an average size ranging from about 1 15 to about 125 microns.

[0092] Embodiment 30. The method of any one of embodiments 20-29, further comprising cleaning the damage site before applying the composition.

[0093] Embodiment 31 . The method of embodiment 30, wherein the cleaning comprises sand blasting, grit blasting, or a combination of both. [0094] Embodiment 32. The method of any one of embodiments 20-31 , wherein the frit material further comprises calcium oxide, cobalt oxide, nickel oxide, manganese oxide, lithium oxide, sodium oxide, rubidium oxide, cesium oxide, francium oxide, or a combination thereof.

[0095] Embodiment 33. A method of preparing a chemically-resistant coating on a substrate, comprising:

applying a composition to the substrate, wherein the composition:

(a) comprises a ground coat material in the form of particles having a particle size distribution such that at least about 5 weight percent of the particles are smaller than 44 microns and at least about 20 weight percent of the particles are larger than 150 microns, and

(b) the ground coat material comprises a frit material comprising from about 48 to about 58 weight percent of silica, from about 12 to about 22 weight percent of boric oxide, from about 1 to about 9 weight percent of potassium oxide, and from about 1 to about 9 weight percent of alumina;

firing the composition to form a softened ground coat on the substrate;

flame-spray depositing a coating material onto the softened ground coat, wherein the coating material:

(a) is in the form of particles having an average size ranging from about 74 to about 177 microns, and

(b) comprises from about 68 to about 74 weight percent of silica, from about 0.5 to about 2.5 weight percent of alumina, from about 7 to about 15 weight percent of sodium oxide, from about 1 to about 5 weight percent of lithium oxide, and from about 2 to about 9 weight percent of zirconium oxide; and cooling the substrate slowly, thereby preparing the chemically-resistant coating on the substrate.

[0096] Embodiment 34. The method of embodiment 33, wherein the firing comprises applying induction heating.

[0097] Embodiment 35. The method of any one of embodiments 33-34, wherein the cooling the substrate slowly comprises applying induction heating.

[0098] Embodiment 36. The method of any one of embodiments 33-35, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than thirty minutes after the flame-spray depositing.

[0099] Embodiment 37. The method of any one of embodiments 33-36, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than one hour after the flame-spray depositing.

[00100] Embodiment 38. The method of any one of embodiments 33-37, wherein cooling the substrate slowly comprises allowing the substrate to pass through the glass transition temperature of the coating material in a time period of not less than two hours after the flame-spray depositing. [00101] Embodiment 39. The method of any one of embodiments 33-38, wherein the composition is in the form of a slurry and comprises from about 30 to about 40 weight percent liquid.

[00102] Embodiment 40. The method of embodiment 39, wherein the liquid comprises water.

[00103] Embodiment 41 . The method of any one of embodiments 33-40, further comprising drying the composition before the firing.

[00104] Embodiment 42. The method of any one of embodiments 33-41 , wherein the coating material in the form of particles has an average size ranging from about 1 15 to about 125 microns.

[00105] Embodiment 43. The method of any one of embodiments 33-42, further comprising cleaning the substrate before applying the composition.

[00106] Embodiment 44. The method of embodiment 43, wherein the cleaning comprises sand blasting, grit blasting, or a combination of both.

[00107] Embodiment 45. The method of any one of embodiments 33-44, wherein the frit material further comprises calcium oxide, cobalt oxide, nickel oxide, manganese oxide, lithium oxide, sodium oxide, rubidium oxide, cesium oxide, francium oxide, or a combination thereof. [00108] Embodiment 46. An article comprising:

(a) a metal substrate;

(b) a ground coat comprising silica, boric oxide, potassium oxide, and alumina; and

(c) a coating in the form of splats comprising silica, alumina, sodium oxide, lithium oxide, and zirconium oxide.

[00109] Embodiment 47. The article of embodiment 46, wherein the metal substrate comprises steel.

[001 10] Embodiment 48. The article of any one of embodiments 46-47, wherein the splats have an average volume ranging from about 2.1 x 10 ^"13 m ³ to about 2.9 x 10 ^"12 m ³ .

[001 11] Embodiment 49. The article of any one of embodiments 46-48, wherein the splats have an average volume ranging from about 2.1 x 10 ^"13 m ³ to about 1 .7 x 10 ^"12 m ³ .

[001 12] Embodiment 50. The article of any one of embodiments 46-49, wherein the splats have an average volume ranging from about 7.9 x 10 ^"13 m ³ to about 1 .0 x 10 ^"12 m ³ .

[001 13] Embodiment 51 . The article of any one of embodiments 46-50, wherein the article is a reactor vessel. [001 14] Embodiment 52. The article of any one of embodiments 46-50, wherein the article is a cover.

[001 15] Embodiment 53. The article of any one of embodiments 46-50, wherein the article is a baffle.

[001 16] Embodiment 54. The article of any one of embodiments 46-50, wherein the article is a thermowell.

[001 17] Embodiment 55. The article of any one of embodiments 46-50, wherein the article is an agitator.

[001 18] Embodiment 56. The article of any one of embodiments 46-50, wherein the article is an agitator shaft.

[001 19] Embodiment 57. The article of any one of embodiments 46-50, wherein the article is a pipe.

[00120] Embodiment 58. The article of any one of embodiments 46-50, wherein the article is a heat exchanger.

[00121] Embodiment 59. The article of any one of embodiments 46-50, wherein the article is a storage tank. [00122] Embodiment 60. The article of any one of embodiments 46-59, wherein the ground coat comprises from about 60 to about 65 weight percent of silica.

[00123] Embodiment 61 . The article of any one of embodiments 46-60, wherein the ground coat comprises from about 10 to about 22 weight percent of boric oxide.

[00124] Embodiment 62. The article of any one of embodiments 46-61 , wherein the ground coat comprises from about 1 to about 9 weight percent of potassium oxide.

[00125] Embodiment 63. The article of any one of embodiments 46-62, wherein the ground coat comprises from about 1 to about 9 weight percent of alumina.

[00126] Embodiment 64. The article of any one of embodiments 46-63, wherein the ground coat comprises calcium oxide, cobalt oxide, nickel oxide, manganese oxide, one or more alkali metal oxides in addition to potassium oxide, a combination thereof.

[00127] Embodiment 65. The article of any one of embodiments 46-64, wherein the coating in the form of splats comprises from about 68 to about 74 wei percent of silica. [00128] Embodiment 66. The article of any one of embodiments 46-65, wherein the coating in the form of splats comprises from about 0.5 to about 2.5 weight percent of alumina.

[00129] Embodiment 67. The article of any one of embodiments 46-66, wherein the coating in the form of splats comprises from about 7 to about 15 weight percent of sodium oxide.

[00130] Embodiment 68. The article of any one of embodiments 46-67, wherein the coating in the form of splats comprises from about 1 to about 5 weight percent of lithium oxide.

[00131] Embodiment 69. The article of any one of embodiments 46-68, wherein the coating in the form of splats comprises from about 2 to about 9 weight percent of zirconium oxide.

[00132] As previously stated, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various forms. It will be appreciated that many modifications and other variations are within the intended scope of this invention as claimed below. Furthermore, the foregoing description of various embodiments does not necessarily imply exclusion. For example, "some" embodiments may include all or part of "other" and "further" embodiments within the scope of this invention. In addition, "a" does not mean "one and only one;" "a" can mean "one and more than one."