• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Ceramic composition for the coating of metallic surfaces, method and resulting ceramic layer, referred to a ceramic composition that is subjected after its deposition to a thermal treatment to generate a ceramic layer. The resulting ceramic layer has, among other characteristics, a correct adhesion to the metal surface and the property of remaining unchanged at temperatures between 750ºC and 950º c. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2597166A1
    申请号:ES201530838
    申请日:2015-06-16
    公开日:2017-01-16
    发明作者:Carlos CONCEPCIÓN HEYDORN；Vicente FERRANDO CATALÁ；Juan Vicente Corts Ripoll；Óscar RUIZ VEGA
    申请人:Torrecid SA；
    IPC主号:
    专利说明:

    5
    10
    fifteen
    twenty
    25
    30
    35
    CERAMIC COMPOSITION FOR THE COATING OF METAL SURFACES, METHOD AND CERAMIC LAYER RESULT
    DESCRIPTION
    The invention relates to new ceramic compositions for application on metal surfaces. More particularly on metal surfaces subjected to working temperatures between 750 ° C and 950 ° C. It also refers to a method of coating a metal surface and the ceramic layer resulting from said process.
    The present invention falls within the industrial sector of surface metal treatments.
    STATE OF THE TECHNIQUE
    Metal surfaces are currently used in numerous products and applications. Given the characteristics of metal substrates, in many cases it is necessary to reinforce the metal surface with a coating in order to improve its properties such as impermeability, resistance to chemical agents, resistance to corrosion, resistance to stains or food , among other. One of the ways is the deposition of frits or inorganic compositions that are applied by different techniques (airbrushing, screen printing, enamelling, electrostatic deposition,
    immersion coating, etc.). Subsequently, the metal surface is subjected to a thermal treatment that gives the deposited layer adequate adhesion to the surface.
    Thus, US5296415 describes a composition based exclusively on the use of a frit containing in its composition CeO2 in a weight percentage comprised between 2.5% and 9% in order to provide a high refractive index, as well as adhesion and acid resistance However, the frit composition according to US5296415 has low softening point temperatures, around 500 ° C, as indicated in example 1 of said patent. This, together with the fact that the composition contains only fried, indicates that it cannot be used as a coating of metallic surfaces subjected to a working temperature equal to or greater than 750 ° C, since properties such as the absence of porosity, resistance are lost to acids, bases, molten salts, among others. Likewise, US5296415 patent includes the incorporation in the
    5
    10
    fifteen
    twenty
    25
    30
    35
    frit of F compounds in a weight percentage between 0.3% and 5% to improve adhesion to the metal surface, which causes acidic compounds that are harmful to the environment to be emitted during cooking and that deteriorate the systems of gas purification.
    For its part, patent application US2014 / 0302331A1 describes a composition of frit and additives that, once applied on the metal surface and heat treatment, provides a surface for domestic ovens that prevents food adhesion during the cooking process. However, the composition of the frit and the presence of F compounds as additives, as described in US2014 / 0302331A1, indicates that the composition begins to melt below 600 ° C, so it cannot be Use on metal surfaces that require to remain unchanged at temperatures of 750 ° C or higher. In addition, the invention according to the application US2014 / 0302331A1 contains as additives compounds of F and NO2, which causes acidic compounds and nitrogen oxides harmful to the environment to be emitted during cooking and which deteriorate the gas purification systems. Finally, it should also be noted that the application US2014 / 0302331A1 requires two applications or layers called "ground coat" and "cover coat" to achieve the desired properties, which increases the cost against a single application.
    Another example of the state of the art is the patent application US2007 / 0265154 where an enamel with metallic appearance is described which is subjected to a thermal treatment between 760 ° C and 870 ° C. Said enamel composition contains one or more frits with a melting temperature between 704 ° C and 927 ° C, grinding additives and, optionally, a pigment. Also, the composition of the frits according to the application US2007 / 0265154, also comprises compounds of F and NO2. From US2007 / 0265154 it follows that the enamel composition has a softening temperature not exceeding 750 ° C, so its use is unfeasible for metal surfaces subjected to working temperatures exceeding said temperature. Once again, and as an additional fact, the presence of compounds of F and NO2 causes acidic compounds and nitrogen oxides that are harmful to the environment to be emitted during cooking and deteriorate the gas purification systems.
    EXPLANATION OF THE INVENTION
    5
    10
    fifteen
    twenty
    25
    30
    The present invention provides a ceramic composition, without compounds of F and NO2, intended for coating metal surfaces. The resulting coating, called ceramic layer, has, among other features, a correct adhesion to the metal surface and the property of remaining unchanged at temperatures between 750 ° C and 950 ° C, thus overcoming the limitations of the state of the art previous. In this sense, the ceramic composition object of the invention is especially intended for those applications where metal surfaces that resist high working temperatures are required, as well as resistance to acids, bases, molten salts, aggregates and / or fossil fuels, among others . Such is the case of deposits of chemical products, deposits of molten salts and oils for applications in solar thermal energy, conduits for oil extraction and heat exchangers, among others.
    According to the present invention, the ceramic composition contains at least one or more frits with a softening temperature greater than 675 ° C and whose weight percentage is between 40% and 82%. Also the frit or mixture of frits comprises between 55% and 70% by weight of SiO2, between 7% and 20% by weight of R2O, between 0% and 15% by weight of RO, between 0% and 8% by weight of MOx, between 0% and 7% by weight of MO2, between 0.5% and 8% by weight of Al2O3 and between 3% and 10% by weight of B2O3. The R2O formula represents at least one oxide selected from Li2O, Na2O and K2O or mixture thereof. The RO formula represents at least one oxide selected from ZnO, MgO, CaO and BaO or mixture thereof. The MOx formula represents at least one oxide selected from CuO, MnO2, Fe2O3, MoO3, CoO and NiO or mixture thereof. The MO2 formula represents at least one oxide selected from TiO2 and CeO2 or mixture thereof.
    Another aspect of the ceramic composition object of the invention is that it contains at least one or more refractory compounds with a melting point greater than 1,600 ° C and whose weight percentage is between 15% and 50%. The term "refractory compound" as used in the present invention refers to any inorganic compound, present in nature or obtained industrially, which has the property of withstanding high temperatures remaining unchanged and not decomposing. The refractory compound according to the present invention is selected from ZrO2, Cr2O3, Al2O3, SiO2, ZrSiO4, Mullita, compounds containing Zr and / or Cr and / or Cu, or mixture thereof, Preferably, the refractory compound according to the present invention includes ZrO2 and / or Cr2O3 , alone or mixed with each other or with Al2O3, SiO2, ZrSiO4, Mullita or compounds that
    5
    10
    fifteen
    twenty
    25
    30
    contain Zr and / or Cr and / or Cu. The presence of ZrO2 and / or Cr2O3 in the ceramic composition guarantees the stability of the ceramic layer at high temperatures, thus improving the coatings existing in the state of the art.
    A third feature of the present invention is that it comprises at least one or more synthetic compounds whose weight percentage is between 3% and 10% and contains in its composition Co or Ni or Cu or Fe or Mo or Mn or Cr, or mix them. The term "synthetic compound" as used in the present invention refers to any inorganic compound in powder form obtained from a chemical reaction at a certain temperature and the reagents being in a solid and / or liquid state.
    The method of coating the metal surface for the formation of the ceramic layer comprises two stages. The first stage consists in depositing the ceramic composition on the metal surface. In this sense, the ceramic composition according to the present invention can be applied by any of the techniques of enamelling or coating of existing metal surfaces, both dry and wet. Examples of these techniques, by way of example but not limitation, are airbrushing, dip coating (dip coating), screen printing, inkjet, pad printing, electrophoresis and / or dry enameling by electrostatic application, among others. The second stage consists in 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 said maximum temperature, between 2 and 10 minutes. Therefore, the thermal treatment converts the ceramic composition into a uniform ceramic layer, which has a correct adhesion to the metal substrate, a softening temperature between 850 ° C and 960 ° C, a thermal expansion coefficient at 300 ° C comprised between 80x10-7 ° C-1 and 100x10-7 ° C-1 and the property of remaining unchanged at temperatures between 750 ° C and 950 ° C. The term "'' inalterable" referring to the ceramic layer, as used in the present invention, means a layer or a coating that has a correct adhesion to the metal substrate and is physically and chemically stable, so that its properties are not they vary
    A preferred embodiment of the present invention consists of a ceramic composition comprising between 60% and 70% by weight of a mixture of two frits with a superheating temperature greater than 700 ° C, between 25% and 40% by weight of two compounds
    5
    10
    fifteen
    twenty
    25
    30
    refractories with a melting temperature higher than 1,600 ° C and containing Zr and Cr in their composition, and between 3% and 10% by weight of a synthetic compound containing Cu, Cr and Mn in their composition. The ceramic composition is deposited on the metal surface by any of the enamelling techniques existing in the state of the art. The amount deposited, expressed in grams of solids, is between 100 g / m2 and 500 g / m2, preferably between 200 g / m2 and 350 g / m2. Subsequently, it is subjected to a thermal treatment at a maximum temperature between 910 ° C and 960 ° C for 3 minutes. The ceramic layer obtained has a softening temperature between 870 ° C and 930 ° C and a thermal expansion coefficient at 300 ° C between 80x10-7 ° C-1 and 100x10-7 ° C-1.
    Another preferred embodiment of the present invention consists of a ceramic composition comprising between 60% and 80% by weight of a frit with a softening temperature greater than 800 ° C, between 25% and 40% by weight of a refractory compound with a melting temperature higher than 1,600 ° C and containing in its composition Cr2O3 and / or ZrO2, alone or mixed with SiO2, and between 5% and 10% by weight of a synthetic compound that contains in its composition Co or Cu or Fe or Mo or Mn or Cr or mix them. The ceramic composition is deposited on the metal surface by any of the enamelling techniques existing in the state of the art. The amount deposited, expressed in grams of solids, is between 100 g / m2 and 500 g / m2, preferably between 200 g / m2 and 350 g / m2. Subsequently, it is subjected to a thermal treatment at a maximum temperature between 910 ° C and 960 ° C for 3 minutes. The ceramic layer obtained has a softening temperature between 850 ° C and 890 ° C and a thermal expansion coefficient at 300 ° C between 80x10-7 ° C-1 and 100x10-7 ° C-1.
    Throughout the description and the claims, the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. In addition, the word "includes" includes the case "consists of". the matter, other objects, advantages and characteristics of the invention will be derived partly from the description and partly from the practice of the invention.
    PREFERRED EMBODIMENTS OF THE INVENTION
    5
    10
    fifteen
    twenty
    25
    30
    The following examples are provided by way of illustration, and are not intended to be limiting of the present invention. In addition, the present invention covers all possible combinations of particular and preferred embodiments indicated herein.
    In the embodiments of the invention detailed below, the various components of the ceramic composition are indicated. In all cases, the procedure consisted of preparing the corresponding ceramic composition and depositing it by means of a specific application technique on a metal surface. Depending on the technique, together with the ceramic composition, the necessary components for its correct application such as solvents and additives, widely known in the state of the art, were included. Subsequently, the metal surface, together with the deposited ceramic composition, was subjected to a thermal treatment to obtain the ceramic layer responsible for conferring to the metal surface the properties described throughout the present invention.
    The evaluation of the results consisted of carrying out a series of tests on metallic pieces once the ceramic composition was deposited and the thermal treatment was carried out, that is, the metallic surface with the ceramic layer, as described in the present invention. The tests are described below.
    -Determination of resistance to dric acid at room temperature. According to UNE-EN ISO28706-1: 2008.
    -Determination of sulfuric acid resistance at room temperature. According to UNE-EN ISO28706-1: 2008.
    -Determination of sulfuric acid resistance in boiling. According to UNE-EN ISO 28706-2: 2008.
    -Determination of resistance to chlortidic acid in boiling. According to UNE-EN ISO 28706-2: 2008.
    -Resistance to molten salts. A metal piece was taken and the initial thickness and mass measured. Then a 200 mg cylindrical tablet composed of a mixture of 60% by weight NaNO3 and 40% by weight of KNO3 was deposited on said metal part and
    5
    10
    fifteen
    twenty
    25
    I leave in contact at 600 ° C for 24 hours, followed by cooling at 25 ° C for 30 minutes. Subsequently, the piece was washed with distilled water until there were no remains of the tablet, dried at 100 ° C for 30 minutes and finally the stain resistance was evaluated according to ISO 10545-14: 1998.
    -Adhesion to the metal substrate. According to standard UNE-EN10209: 2013.
    -Thermal resistance. A metal piece was taken and the roughness and initial mass measured. It was then placed in a laboratory oven at 700 ° C for 90 hours followed by cooling at 25 ° C for 30 minutes. Subsequently, the surface roughness and mass of the piece were measured. If the weight loss was less than 0.05% and / or the surface roughness of less than 1 micrometer is considered passed the test.
    - Resistance to stains. According to ISO10545-14: 1998.
    Example 1
    First, two frites called F1 and F2 were melted whose oxide compositions were varied depending on the desired thermal properties (softening temperature,% sphere temperature and fluidity temperature). Specifically, the oxide compositions of both frits comprise between 55% and 70% by weight of SiO2, between 7% and 20% by weight of R2O, between 0% and 15% by weight of RO, between 0% and 8% by weight of MOx, between 0% and 7% by weight of MO2, between 0.5% and 8% by weight of Al2O3 and between 3% and 10% by weight of B2O3; where R2O represents at least one oxide selected from Li2O, Na2O and K2O or mixture thereof, where RO represents at least one oxide selected from ZnO, MgO, CaO and BaO or mixture thereof, where MOx represents at least one oxide selected from CuO , MnO2, Fe2O3, MoO3, CoO and NiO or mixture thereof and where MO2 represents at least one oxide selected from TiO2 and CeO2 or mixture thereof. Table 1 shows the thermal properties of frits F1 and F2.
    Table 1
     F1 F2
     T. softening (° C)  700 715
     T.% sphere (° C)  792 876
     T. fluidity (° C)  828 968
    5
    10
    fifteen
    twenty
    25
    The two frits were prepared using conventional industrial frit fusion techniques. For this purpose, the different precursor raw materials of the oxides were mixed according to the composition of the frit. This mixture was then melted in an industrial oven at the typical temperatures of this process, using a mixture of gas and oxygen. The molten mixture cooled rapidly in a bath of water forming the frit.
    Based on frits F1 and F2, three ceramic compositions called C1, C2 and C3 were prepared. The three compositions were adapted for correct application by airbrushing. In all cases 250 g / m2, expressed as grams of solids, were deposited on a metallic surface of AISI 316 steel. The thermal treatment was in all cases at a maximum temperature of 960 ° C for 3 minutes. Table 2 shows each of the compositions as well as the softening temperature and the thermal expansion coefficient of the ceramic layer obtained.
    Table 2
     Component  Denomination C1 C2 C3
     Fried  F1 100 28 25
     Fried  F2 42 45
     Refractory compound  Mullita - 10 15
     Refractory compound  A ^ O3 - 20 10
     Synthetic compound  MoO3 - 5
     T. Ceramic layer softening (° C)  705 824 940
     Coefficient of thermal expansion at 300 ° C (x10-7 ° C-1)  96 89 90
    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 that obtained from composition C3 passed all the tests.
    Table 3
     Test  C1 C2 C3
     Dric acid resistance  AA AA AA
     Sulfuric acid resistance  AA AA AA
     Boiling sulfuric acid resistance (g / m2)  <1.6 <1.6 <1.6
     Boiling hydrochloric acid resistance (g / m2)  <1.6 <1.6 <1.6
     Resistance to molten salts  1 3 5
     Adhesion to the metal substrate  Class 1 Class 3 Class 1
     Thermal resistance at 700 ° C  No No Yes
     Stain resistance  1 4 5
    Example 2
    5 Two frits called F3 and F4 were melted whose oxide compositions were varied depending on the desired thermal properties (softening temperature,% sphere temperature and fluidity temperature). Specifically, the oxide compositions of both frits comprise between 55% and 70% by weight of SiO2, between 7% and 20% by weight of R2O, between 0% and 15% by weight of RO, between 0% and 8% in weight of MOx, between 0% and 10 7% by weight of MO2, between 0.5% and 8% by weight of Al2O3 and between 3% and 10% by weight of B2O3;
    where R2O represents at least one oxide selected from Li2O, Na2O and K2O or mixture thereof, where RO represents at least one oxide selected from ZnO, MgO, CaO and BaO or mixture thereof, where MOx represents at least one oxide selected from CuO , MnO2, Fe2O3, MoO3, CoO and NiO or mixture thereof and where MO2 represents at least one oxide selected from TiO2 and CeO2 or mixture thereof. Table 4 shows the thermal properties of frits F3 and F4.
    Table 4
     F3 F4
     T. softening (° C)  829 755
     T.% sphere (° C)  930 844
     T. fluidity (° C)  1029 860
    A composition called C4 was prepared. Composition C4 was adapted for correct application by dip coating and 250 g / m2, expressed as grams of solids, were deposited on a metallic surface of AISI 310 steel. The application was subjected to a thermal treatment with a maximum temperature of 940 ° C 5 for 3 minutes. Table 5 shows the composition C4 as well as the softening temperature and the coefficient of thermal expansion of the ceramic layer obtained.
    Table 5
     Component  Denomination C4
     Fried  F3 48
     Fried  F4 30
     Refractory compound  SiO2 7
     Refractory compound  Cr2ZrO5 8
     Synthetic compound  (FeCr) (CoNi) 2O4 7
     T. Ceramic layer softening (° C)  940
     Coefficient of thermal expansion at 300 ° C (x10-7 ° C-1)  94
    10 Table 6 shows that the ceramic layer obtained from composition C4 passed all the tests.
    Table 6
     Test  C4
     Dric acid resistance  AA
     Sulfuric acid resistance  AA
     Boiling sulfuric acid resistance (g / m2)  <1.6
     Boiling hydrochloric acid resistance (g / m2)  <1.6
     Resistance to molten salts  5
     Adhesion to the metal substrate  Class 1
     Thermal resistance at 700 ° C  Yes
     Stain resistance  5
    Example 3
    Three compositions called C5, C6 and C7 were prepared and adapted for proper application by Electrophoretic Deposition. In all cases, 5 200 g / m2, expressed as grams of solids, were deposited on a metal surface of AISI steel
    310. In all three cases a thermal treatment was carried out at a maximum temperature of 955 ° C for 3 minutes. Table 7 shows the three compositions as well as the softening temperature and the thermal expansion coefficient of the ceramic layer obtained in each case.
    10
    Table 7
     Component  Denomination C5 C6 C7
     Fried  F1 26 25
     Fried  F2 38 37
     Fried  F3 75
     Refractory compound  Cr2O3 18 15
     Refractory compound  ZrO2 12
     Refractory compound  Cr2ZrO5 28
     Synthetic compound  (CuCrMn) 2O 6 10 10
     T. Ceramic layer softening (° C)  880 900 875
     Coefficient of thermal expansion at 300 ° C (x10-7 ° C-1)  89 90 93
    Table 8 shows that the ceramic layers obtained from compositions C5, C6 and C7 passed all tests.
    Table 8
     Test  C5 C6 C7
     Dric acid resistance  AA AA AA
     Sulfuric acid resistance  AA AA AA
     Boiling sulfuric acid resistance (g / m2)  <1.6 <1.6 <1.6
     Boiling chlortidic acid resistance (g / m2)  <1.6 <1.6 <1.6
     Resistance to molten salts  5 5 5
     Adhesion to the metal substrate  Class 1 Class 1 Class 1
     Thermal resistance at 700 ° C  Yes Yes Yes
     Stain resistance  5 5 5
    权利要求:
    Claims (12)
    [1]
    5
    10
    fifteen
    twenty
    25
    30
    35
    1. A ceramic composition for coating metal surfaces by means of a thermal treatment comprising:
    to. At least one fry whose weight percentage is between 40% and 82%,
    b. At least one refractory compound with a melting temperature greater than 1600 ° C, and
    C. At least one synthetic compound that contains in its composition Co or Ni or Cu or Fe or Mo or Mn or Cr or a mixture thereof.
    [2]
    2. The ceramic composition according to claim 1 wherein the composition by weight of the at least one frit comprises between 55% and 70% of SiO2, between 7% and 20% of R2O, between 0% and 15% of RO, between 0 % and 8% of MOx, between 0% and 7% of MO2, between 0.5% and 8% of Al2O3 and between 3% and 10% of B2O3; where R2O represents at least one oxide selected from Li2O, Na2O and K2O or mixture thereof, where RO represents at least one oxide selected from ZnO, MgO, CaO and BaO or mixture thereof, where MOx represents at least one oxide selected from CuO , MnO2, Fe2O3, MoO3, CoO and NiO or mixture thereof and where MO2 represents at least one oxide selected from TiO2 and CeO2 or mixture thereof.
    [3]
    3. The ceramic composition according to claim 1 wherein the weight percentage of the mixture of one or more refractory compounds is between 15% and 50%.
    [4]
    4. The ceramic composition according to the preceding claim wherein the mixture of one or more refractory compounds is selected from ZrO2, Cr2O3, Al2O3, SiO2, ZrSiO4, Mullite, compounds containing Zr and / or Cr and / or Cu, or mixture of they.
    [5]
    5. The ceramic composition according to claim 1 wherein the percentage by weight of the mixture of one or more synthetic compounds is between 3% and 10%.
    [6]
    6. The ceramic composition according to claim 1 characterized in that its softening temperature after heat treatment is between 850 ° C and 960 ° C.
    5
    10
    fifteen
    twenty
    25
    [7]
    7. The ceramic composition according to claim 1 characterized in that its thermal expansion coefficient at 300 ° C after the heat treatment is between 80x10-7 ° C-1 and 100x10-7 ° C-1.
    [8]
    8. The ceramic composition according to claim 1 wherein the at least one frit has a softening temperature greater than 675 ° C.
    [9]
    9. Method of coating a metal surface for the formation of a ceramic layer, characterized in that it comprises the steps of:
    - Deposit a ceramic composition according to claim 1 on the metal surface, and
    - Subject said surface to a thermal treatment with a maximum temperature of 980 ° C for a maximum time of 10 minutes.
    [10]
    10. The method, according to claim 9, characterized in that the ceramic composition is deposited by the technique of airbrushing, curtain enamelling, inkjet, electrostatic deposition, electrophoretic deposition, silkscreen, immersion coating, hollow, flexography, pad printing or brush .
    [11]
    11. The ceramic layer, according to the method of claim 9 and 10, characterized in that it comprises a softening temperature between 850 ° C and 960 ° C.
    [12]
    12. The ceramic layer, according to the method of claim 9 and 10, characterized in that it comprises a thermal expansion coefficient at 300 ° C comprised between 80x10 "7 ° C-1 and 100x10" 7 ° C-1.
    类似技术:
    公开号 | 公开日 | 专利标题
    US7695831B2|2010-04-13|Coating composition, and cooking device or cooking receptacle coated with the same
    US6001494A|1999-12-14|Metal-ceramic composite coatings, materials, methods and products
    Bakan et al.2015|Porosity–property relationships of plasma‐sprayed Gd2Zr2O7/YSZ thermal barrier coatings
    ES2741880T3|2020-02-12|Base coat and enamel compositions
    CN101570397B|2011-06-08|Porcelain enamel with superior adherence and acid resistance simultaneously and preparation method thereof
    ES2615529T3|2017-06-07|Cooking appliance that includes glass composition
    US3203815A|1965-08-31|High-temperature protective coating for metals
    WO1999012857A1|1999-03-18|Reflective porcelain enamel coating composition
    ES2597166B1|2017-11-06|CERAMIC COMPOSITION FOR THE COATING OF METAL SURFACES, METHOD AND RESULTING CERAMIC LAYER
    US3891452A|1975-06-24|Refractory porcelain enamel passive control coating for high temperature alloys
    US2842458A|1958-07-08|Low temperature vitreous coatings for steel
    US2846325A|1958-08-05|Refractory vitreous ceramic coating materials
    US2829062A|1958-04-01|Refractory vitreous ceramic coating materials
    Ndamka et al.2016|The degradation of thermal barrier coatings by molten deposits: introducing the concept of basicity
    ES2609262T3|2017-04-19|Non-enameled enameled sheet steel
    Hossain et al.2014|Vitreous enamel coating on mild steel substrate: characterization and evaluation
    Izgagina et al.2018|Composition Development and Property Study of Alkali-Resistant Enamel for the Protection of Chemical Apparatus
    Kassem et al.2010|Hot water acid‐resistant enamels for sheet steel
    JP2010228968A|2010-10-14|Frit for enamel
    RU2255076C1|2005-06-27|Heat-resistant coating
    CN212871508U|2021-04-02|Thermocouple with high-temperature resistant enamel protective layer
    RU2598657C1|2016-09-27|Heat-resistant cover
    ES2687800A1|2018-10-29|COMPOSITION AND CONFORMING OF CERAMIC MATERIAL OF LOW COEFFICIENT OF THERMAL DILATION AND ELEVATED RESISTANCE TO THE THERMAL SHOCK |
    CA2037372A1|1991-09-09|Enamel compositions
    RU2239616C2|2004-11-10|Refractory coating
    同族专利:
    公开号 | 公开日
    EP3312146A1|2018-04-25|
    ES2597166B1|2017-11-06|
    US10336649B2|2019-07-02|
    US20180141852A1|2018-05-24|
    WO2016203075A1|2016-12-22|
    EP3312146A4|2019-03-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2020099704A1|2018-11-12|2020-05-22|Torrecid, S.A|Ink composition decorating tableware|US3203815A|1962-12-21|1965-08-31|North American Aviation Inc|High-temperature protective coating for metals|
    US3184320A|1964-12-08|1965-05-18|North American Aviation Inc|Ceramic protective coating composition|
    US3285773A|1965-05-10|1966-11-15|Ferro Corp|Vitreous enamels for hot water tanks|
    JPS5542944B2|1976-04-20|1980-11-04|
    US4385127A|1981-11-23|1983-05-24|Corning Glass Works|Glass-ceramic coatings for use on metal substrates|
    US5250360A|1987-11-16|1993-10-05|Corning Incorporated|Coated metal article|
    DE4124801C2|1991-07-26|1995-03-30|Bayer Ag|Enamel frit for direct enameling on unpainted steel sheet and its use|
    DE69617084T2|1995-04-24|2002-06-20|Corning Inc|Methods for protecting metals|
    US20040232576A1|1999-07-02|2004-11-25|Dmtri Brodkin|Method of making dental restorations|
    US7410672B2|1999-10-12|2008-08-12|Aos Holding Company|Water-resistant porcelain enamel coatings and method of manufacturing same|
    US6423415B1|2000-08-31|2002-07-23|Corning Incorporated|Potassium silicate frits for coating metals|
    US7763557B2|2005-05-12|2010-07-27|Ferro Corporation|Porcelain enamel having a metallic appearance|
    US8778455B2|2010-04-27|2014-07-15|Ferro Corporation|Enamel and ground coat compositions|
    US9296643B2|2012-05-10|2016-03-29|Lg Electronics Inc.|Enamel composition, preparation method thereof, and cooking appliance including the same|
    法律状态:
    2017-11-06| FG2A| Definitive protection|Ref document number: 2597166 Country of ref document: ES Kind code of ref document: B1 Effective date: 20171106 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201530838A|ES2597166B1|2015-06-16|2015-06-16|CERAMIC COMPOSITION FOR THE COATING OF METAL SURFACES, METHOD AND RESULTING CERAMIC LAYER|ES201530838A| ES2597166B1|2015-06-16|2015-06-16|CERAMIC COMPOSITION FOR THE COATING OF METAL SURFACES, METHOD AND RESULTING CERAMIC LAYER|
    US15/578,294| US10336649B2|2015-06-16|2016-05-27|Ceramic composition for coating metallic surfaces, method and resulting ceramic layer|
    PCT/ES2016/070401| WO2016203075A1|2015-06-16|2016-05-27|Ceramic composition for coating metallic surfaces, method and resulting ceramic layer|
    EP16811066.6A| EP3312146A4|2015-06-16|2016-05-27|Ceramic composition for coating metallic surfaces, method and resulting ceramic layer|
    [返回顶部]