Patent Application
20180141852
The invention discloses new ceramic compositions for application on metallic surfaces. More specifically, on metallic surfaces subjected to operating temperatures between 750° C. and 950° C. It likewise discloses a method for coating a metallic surface and the ceramic layer resulting from said process.
The present invention falls within the industrial sector of surface treatments of metals.
Metallic surfaces are currently used in numerous products and applications. Given the characteristics of metallic substrates, in many cases the metallic surface must be reinforced with a coating in order to improve its properties, such as water resistance, resistance to chemical agents, corrosion resistance, and resistance to stains or food, among others. One of the methods consists of the deposition of frits or inorganic compositions that are applied using different techniques (aerography, silk-screening, enamelling, electrostatic deposition, immersion coating, etc.). The metallic surface is later subjected to a thermal treatment that gives the deposited layer the necessary adhesion to the surface.
U.S. Pat. No. 5,296,415 describes a composition based exclusively on the use of a frit that contains CeO2 in its composition, in a percentage by weight between 2.5% and 9%, in order to provide a high refraction index, as well as adherence and acid resistance. However, the composition of the frit as described in U.S. Pat. No. 5,296,415 presents softening point temperatures of around 500° C., as indicated in example 1 of the aforementioned patent. This, together with the fact that the composition only contains frit, indicates that it cannot be used as a coating for metallic surfaces subjected to operating temperatures greater than or equal to 750° C., because it loses its properties, such as the absence of porosity, resistance to acids, bases, molten salts, among others. U.S. Pat. No. 5,296,415 also covers the incorporation of F compounds into the frit, in a percentage by weight between 0.3% and 5%, to improve adhesion to the metallic surface, which causes the generation of acid compounds that are harmful to the environment and that cause deterioration of gas scrubbing systems during firing.
Patent application US2014/0302331A1 describes a frit and additive composition which, after application to the metallic surface and thermal treatment, generates a surface for household ovens that prevents food from sticking during cooking. However, the composition of the frit and the presence of F compounds as additives, as described in patent application US2014/0302331A1, indicate that the composition begins to melt below 600° C., which means that it cannot be used on metallic surfaces that must remain unaltered at temperatures of 750° C. or higher. In addition, the invention according to application US2014/0302331A1 contains F compounds and NO2, which causes the generation of acid compounds and nitrogen oxides that are harmful to the environment and that cause deterioration of gas scrubbing systems during firing. Lastly, it should be noted that application US2014/0302331A1 requires two applications or layers, called the “ground coat” and “cover coat” to achieve the desired properties, which increases the cost in comparison with a single application.
Another example in the prior art is patent application US2007/0265154, which describes an enamel with a metallic appearance that is subjected to a thermal treatment between 760° C. and 870° C. This composition contains one or more frits with melting points between 704° C. and 927° C., grinding additives, and optionally, a pigment. The composition of the frits according to application US2007/0265154, also comprises F compounds and N02. From patent US2007/0265154, it can be deduced that the enamel composition has a softening point of less than 750° C., which makes its use infeasible with metallic surfaces subjected to operating temperatures above that temperature. Once again, and as additional information, the presence of F compounds and NO2 causes the generation of acid compounds and nitrogen oxides that are harmful to the environment and that cause deterioration of gas scrubbing systems during firing.
The present invention provides a ceramic composition, without F compounds and NO2, designed for the coating of metallic surfaces. The resulting coating, called the ceramic layer, presents, among other characteristics, proper adhesion to the metallic surface and remains unaltered at temperatures between 750° C. and 950° C., thus overcoming the limitations of the prior art. In this sense, the ceramic composition that is the object of the invention is especially intended for applications that require metallic surfaces that must withstand high operating temperatures, in addition to resisting acids, bases, molten salts, aggregates and/or fossil fuels, among others. As in the case of tanks for chemical products, molten salt and oil tanks for solar thermal power applications, pipelines for oil extraction and heat exchangers, among others.
According to the present invention, the ceramic composition contains at least one or several frits with softening points above 675° C. and whose percentage by weight is between 40% and 82%. Likewise, the frit or frit mixture comprises Si02 between 55% and 70% by weight, R20 between 7% and 20% by weight, RO between 0% and 15% by weight, MOx between 0% and 8% by weight, MO2 between 0% and 7% by weight, Al203 0.5% and 8% by weight, and B203 between 3% and 10% by weight. The formula R20 represents at least one oxide selected from among Li20, Na20, and K20 or a mixture of them. The formula RO represents at least one oxide selected from among ZnO, MgO, CaO and BaO or a mixture of them. The formula MOx represents at least one oxide selected from among CuO, Mn02, Fe203, Mo03, CoO and NiO or a mixture of them. The formula M02 represents at least one oxide selected between Ti02 and Ce02 or a mixture of them.
Another aspect of the ceramic composition that is the object of the invention is that it contains at least one or more refractory compounds, with melting points above 1,600° C. and whose percentage by weight is between 15% and 50%. The term “refractory compound” as it is used in this invention refers to all inorganic compounds present in nature or obtained industrially, that have the property of resistance to high temperatures, remaining unaltered and without breaking down. The refractory compound according to this invention is selected from among Zr02, Cr203, Al203, Si02, ZrSi04, Mullite, compounds that contain Zr and/or Cr and/or Cu, or a mixture of them. Preferably, the refractory compound according to the present invention includes Zr02 and/or Cr203, alone or mixed together, or with Al203, Si02, ZrSi04, Mullite or compounds that contain Zr and/or Cr and/or Cu. The presences of Zr02 and/or Cr203 in the ceramic composition guarantees the stability of the ceramic layer to high temperatures, thus improving on the existing coatings in the prior art.
A third characteristic of the present invention is that it comprises at least one or more synthetic compounds whose percentage by weight is between 3% and 10% and whose compositions contain Co or Ni or Cu or Fe or Mo or Mn or Cr, or a mixture of them. The term “synthetic compound” as it is used in the present invention refers to all inorganic compounds in powdered form obtained from a chemical reaction at a specific temperature and with the reactants in solid and/or liquid state.
The method for coating the metallic surface for the formation of the ceramic layer comprises two stages. The first stage consists of depositing the ceramic composition on the metallic surface. In this sense, the ceramic composition according to the present invention may be applied using any of the existing techniques, both dry and wet, for enamelling or coating metallic surfaces. Examples of these techniques, for the purposes of example but not limitation, are airbrushing, dip coating, silk-screening, ink injection, pad printing, electrophoresis and/or dry enamelling using electrostatic application, among others. The second stage consists of subjecting the metallic surface obtained in the first stage to a thermal treatment at a maximum temperature between 900° C. and 980° C. for a time, at that maximum temperature, between 2 and 10 minutes. The thermal treatment therefore converts the ceramic composition into a uniform ceramic layer, correctly adhered to the metallic substrate, a softening point between 850° C. and 960° C., a coefficient of thermal expansion at 300° C. between 80×10−7° C.−1 y 100×10−7° C.−1 and the property of remaining unalterable at temperatures between 750° C. and 950° C. The term “inalterable” in reference to the ceramic layer, as it is used in the present invention, means a layer or coating that adheres correctly to the metallic substrate and is physically and chemically stable, so that its properties do not change.
A preferred embodiment of the present invention consists of a ceramic composition that comprises between 60% and 70% by weight of a mixture of two frits with softening points higher than 700° C., between 25% and 40% by weight of two refractory compounds with melting points greater than 1,600° C. and whose compositions contain Zr and Cr, and between 3% and 10% by weight of a synthetic compound whose composition contains Cu, Cr and Mn. The ceramic composition is deposited on the metallic surface using any of the existing enamelling techniques in the prior art. The quantity deposited, expressed in grams of solids, is between 100 g/m2 and 500 g/m2, preferably between 200 g/m2 and 350 g/m2. It is then subjected to a thermal treatment at a temperature between 910° C. and 960° C. for 3 minutes. The obtained ceramic layer has a softening point between 870° C. and 930° C. and a coefficient of thermal expansion at 300° C. between 80×10−7° C.−1 and 100×10−7° C.−1.
Another preferred embodiment of the present invention consists of a ceramic composition that comprises between 60% and 80% by weight of a frit with a softening point above 800° C., between 25% and 40% by weight of a refractory compound with a melting point above 1,600° C. and whose composition contains Cr203 and/or Zr02, alone or mixed with Si02, and between 5% and 10% by weight of a synthetic compound whose composition contains Co or Cu or Fe or Mo or Mn or Cr, or a mixture of them. The ceramic composition is deposited on the metallic surface using any of the existing enamelling techniques in the prior art. The quantity deposited, expressed in grams of solids, is between 100 g/m2 and 500 g/m2, preferably between 200 g/m2 and 350 g/m2. It is then subjected to a thermal treatment at a temperature between 910° C. and 960° C. for 3 minutes. The obtained ceramic layer has a softening point between 850° C. and 890° C. and a coefficient of thermal expansion at 300° C. between 80×10−7° C.−1 and 100×10−7° C.−1.
Throughout the description and the claims, the word “comprises” and its variations are not intended to exclude other technical characteristics, additives, components, or steps. Also, the word “comprises” includes the case of “consists of”. For experts in the subject, other objects, advantages, and characteristics of the invention are drawn from the description and in part from the practical execution of the invention.
The following examples are provide for the purposes of illustration, and are not intended to limit the present invention. In addition, the present invention covers all of the possible combinations of specific and preferred embodiments described here.
The embodiments of the invention that are described below indicate the different components of the ceramic composition. In all cases, the procedure consisted of preparing the corresponding ceramic composition and depositing it on a metallic surface using a particular application technique. Depending on the technique, together with the ceramic composition, the components required for correct application were included, such as solvents and additives, widely known in the state of the art. Later, the metallic surface, together with the deposited ceramic composition, was subjected to a thermal treatment to obtain a ceramic layer responsible for giving the metallic surface the properties described throughout the present invention.
The evaluation of the results consisted of carrying out a series of tests on the metallic pieces after the ceramic composition had been deposited and after the thermal treatment had been applied, in other words, the metallic surface with the ceramic layer, as described in the present invention. The tests are described below.
First, two frits designated F1 and F2 were melted, varying their oxide compositions were based on the desired thermal properties (softening point, ½ sphere temperature, and fluidity temperature). Specifically, the oxide compositions of both frits comprise Si02 between 55% and 70% by weight, R20 between 7% and 20% by weight, RO between 0% and 15% by weight, MOx between 0% and 8% by weight, MO2 between 0% and 7% by weight, Al203 0.5% and 8% by weight, and B203 between 3% and 10% by weight; where R20 represents at least one oxide selected from among Li20, Na20 and K20 OR A mixture of them, where RO represents at least one oxide selected from among ZnO, MgO, CaO and BaO, or a mixture of them, where MOx represents at least one oxide selected from among CuO, Mn02, Fe203, Mo03, CoO and NiO, or a mixture of them, and where MO2 represents at least one oxide selected from between Ti02 and Ce02 or a mixture of them. Table 1 shows the thermal properties of frits F1 and F2.
The two frits are prepared using conventional techniques for melting industrial frit. The different raw materials that were the precursors of the oxides were mixed according to the composition of the frit. The mixture was then melted in an industrial oven at the typical temperatures for this process, using a mixture of gas and oxygen. The molten mixture was quickly cooled in a water bath to form the frit.
Based on frits F1 and F2, three ceramic compositions designated C1, C2 and C3 were prepared. The three compositions were adapted for correct application using airbrushing. In all cases, 250 g/m2, expressed as grams of solids, were applied to a metallic surface of AISI 316 steel. In all cases, the thermal treatment was at a maximum temperature of 960° C. for 3 minutes. Table 2 shows each one of the compositions, as well as the softening point and coefficient of thermal expansion of the obtained ceramic layer.
Table 3 shows the results of the tests. The ceramic layers obtained from compositions C1 and C2 did not pass some of the tests, while the composition obtained with composition C3 passed all of the tests.
Two frits designated F3 and F4 were melted, varying their oxide compositions were based on the desired thermal properties (softening point, ½ sphere temperature, and fluidity temperature). Specifically, the oxide compositions of both frits comprise Si02 between 55% and 70% by weight, R20 between 7% and 20% by weight, RO between 0% and 15% by weight, MOx between 0% and 8% by weight, MO2 between 0% and 7% by weight, Al203 0.5% and 8% by weight, and B203 between 3% and 10% by weight; where R20 represents at least one oxide selected from among Li20, Na20 and K20 or a mixture of them, where RO represents at least one oxide selected from among ZnO, MgO, CaO and BaO, or a mixture of them, where MOx represents at least one oxide selected from among CuO, Mn02, Fe203, Mo03, CoO and NiO, or a mixture of them, and where MO2 represents at least one oxide selected from between Ti02 and Ce02 or a mixture of them. Table 4 shows the thermal properties of frits F3 and F4.
A composition designated C4 was prepared. Composition C4 was adapted for correct application by dip coating, and 250 g/m2, expressed as grams of solids, were applied to a metallic surface of AISI 310 steel. The application was subjected to a thermal treatment at a maximum temperature of 940° C. for 3 minutes. Table 5 shows composition C4, as well as the softening point and coefficient of thermal expansion of the obtained ceramic layer.
Table 6 shows that the ceramic layer obtained from composition C4 passed all of the tests.
Three compositions designated compositions C5, C6 and C7 were prepared and adapted for correct application using Electrophoretic Deposition. In all cases, 200 g/m2, expressed as grams of solids, were applied to a metallic surface of AISI 310 steel. In all three cases, thermal treatment at a maximum temperature of 955° C. was applied for 3 minutes. Table 7 shows each one of the compositions, as well as the softening point and coefficient of thermal expansion of the ceramic layer obtained in each case.
Table 8 shows that the ceramic layers obtained from compositions C5, C6, and C7 passed all of the tests.
| Number | Date | Country | Kind |
|---|---|---|---|
| P201530838 | Jun 2015 | ES | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/ES2016/070401 | 5/27/2016 | WO | 00 |
