US2697670A - Ceramic coated chromium steel - Google Patents
Ceramic coated chromium steel Download PDFInfo
- Publication number
- US2697670A US2697670A US369188A US36918853A US2697670A US 2697670 A US2697670 A US 2697670A US 369188 A US369188 A US 369188A US 36918853 A US36918853 A US 36918853A US 2697670 A US2697670 A US 2697670A
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- chromium
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- enamel
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- 239000000919 ceramic Substances 0.000 title claims description 20
- 229910001220 stainless steel Inorganic materials 0.000 title description 8
- 210000003298 dental enamel Anatomy 0.000 claims description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 21
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 20
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000005524 ceramic coating Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 57
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000002893 slag Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910001610 cryolite Inorganic materials 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- -1 fiuorite Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
- F01D25/007—Preventing corrosion
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D3/00—Chemical treatment of the metal surfaces prior to coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
- C23D5/00—Coating with enamels or vitreous layers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/284—Selection of ceramic materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
- F02C7/30—Preventing corrosion or unwanted deposits in gas-swept spaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
- F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
- Y10S205/917—Treatment of workpiece between coating steps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Definitions
- This invention relates to ceramic-coated chromiumcontaining metallic objects and more particularly to structural parts such as turbine blades which are subject to thermal and mechanical stresses and to the corrosive action of hot gases containing corrosive materials such as vanadium compounds.
- thermally stressed metallic structural elements such as the exhaust pipes of internal combustion engines used on aircraft and the blades of gas turbines with protective layers of ceramic material.
- Such layers serve not only as heat insulation but also to protect the coated surface against corrosion and erosion by hot gases.
- Vanadium compounds when encountered under such conditions, prevent the formation of a protective oxide layer on steels and destroy existing oxide layers so that a progressive oxidation and erosion of steel structural parts such as combustion chamber walls and gas turbine blades which are contacted with combustion gases formed from vanadium containing fuel oils occurs.
- magnesium oxide is strongly resistant to the attack of corrosive slags such as the vanadium containing slag derived from fuel oil.
- Chromium metal also provides a strongly resistant coating. But such protective coatings must adhere strongly to the parts to be protected and this is a problem in the case of the highly heat resistant chromium containing steels.
- An object of the present invention therefore is to provide a strongly adherent and corrosion and erosion resistant coating for chromium containing steel objects and particularly a coating which will withstand the action of vanadium containing slags such as those produced by the combustion of fuel oil.
- a coating of a chromium oxide containing enamel is not particularly resistant to erosion but it has the merit of strong adhesion to the chromium steel surface and the further merit of strong adhesion to a superposed coating or coatings which are resistant to erosion.
- the resulting composite protective coating either with or without the chromium layer has a high heat conductivity and good stability under fluctuating temperature.
- chromium containing steel we mean alloys of chromium with iron containing about 14-30% of chromium and not more than about 0.5% of impurities such as carbon, silicon, manganese, sulfur, phosphorus etc.
- the initial chromium oxide enamel layer should have a heat expansion which is less than that of the chromium steel.
- the steel shrinks more than the enamel and the latter is put under pressure and is much less likely to break than if it were put under tension.
- the chromium oxide enamel is burned onto the surface of the steel and the superposed layers of magnesia containing enamel are each burned onto the preceding layer.
- Fig. l is a diagrammatic section of a protective coating built up entirely of ceramic materials and Fig. 2 is a diagrammatic section of a coating comprising a metallic chromium top layer.
- the coating of Fig. l is formed as follows: A coating layer 2 of chromium oxide enamel composition is applied to the surface of the body 1 of chromium steel having a chromium content of about 21%. This coating should have a heat expansion which is somewhat less than that of the body 1.
- a suitable chromium oxide enamel composition is the following, the parts being by weight. 4 parts of borax, 28 parts of feldspar, 23 parts of quartz, 5 parts of iiuorite, 15 parts of cryolite, 5 parts of soda and 4 parts of chromium oxide.
- the mixture is melted, cooled, pulverized, mixed with water sufcient to form a liquid coating, applied to the steel surface in any suitable manner as by brushing, spraying or dipping, dried and burned or baked at 850 C. to 900 C. for a few minutes.
- a layer 3 of the same enamel composition to which 10% to 20% by weight, based on the weight of the solid components, of magnesium oxide powder has been added is applied, dried and burned in the same way as the layer 2.
- layer 4 is applied, dried and burned,
- said layer consisting of the original enamel composition to which 25 to 35% by Weight of magnesium oxide powder has been added. And finally layer o is applied dr1ed and A burned, said layer consisting ofthe original enamel composition with the addition of 40-60% by weight of magnesium oxide.
- the layers of high magnesium oxide content provide excellent protection of the steel surface against vanadium containing slag.
- the layers adhere well to each other and the base layer 2 adheres well to the steel so that the entire multi-layer coating does not peel or crack even when subjected to sharp temperature changes.
- any desired number of layers may be applied and the magnesium oxide content may be increased to the desired extent by increasing the additions of magnesium oxide to the composition of the rst layer.
- the coating generally is built up to a thickness of at least l mm. and the thickness of the layers and the number thereof may be varied accordingly. It is desirable to increase the magnesia content of the layers by relatively small increments as illustrated but this is not essential as will appear from the following example.
- a layer 2 of the chromium oxide enamel composition described in connection with Fig. 1 is first applied to the chromium steel base 1 and baked. Then a layer 3 of said enamel to which preferably 40 to 60% by weight of magnesium oxide has been added is applied and baked. In effect layers 3 and 4 of Fig. l are omitted. Then the chromium layer 6 is applied by sprinkling metallic chromium in ⁇ powdered form onto the layer 3 while it is at a bright red heat. This results in the chromium being incorporated into the surface of and bonded to the ceramic layer. The resulting coating is particularly advantageous for use in turbine blades.
- the above described coating formed by sprinkling chromium powder upon the hot ceramic layer of ceramic material may be reinforced by electroplating it with chromium.
- the chromium covering layer may be polished leaving the sharp edges in the case of turbine blades, intact. Due to the heat insulating action of the ceramic layer the temperature attained by the metal base of a turbine blade provided with a ceramic coating will be somewhat lower than an unprotected blade subjected to the same gas temperature.
- the ceramic protective coating described above practically eliminates the attack of vanadium containing slags such as are derived from fuel oil. This greatly lengthens the life of combustion chamber walls and other structural parts which are exposed to such slags.
- the invention is not limited to the particular enamel 'compositions vdescribed above.
- the base for vthe chromium oxide containing enamel may be any good enamel suitable for use on unalloyed steel. Many such enamels are well -known. Examples of such enamels Aare the following, the parts being :by weight.
- the chromium oxide content ofthe enamel may vary within the range from 212%.
- An article comprising a metallic object formed of an alloy consisting essentially of iron and from about 14% to about 30% of chromium, anda ceramic'coating on said object said coating comprising a first layer in contact with said object of ceramic enamel substantially free of magnesium oxide and containing from about 2% to ⁇ about 12% of chromium oxide land at least one layer .of ceramic enamel superposed upon said -first layer, said superposed layer containing at least about of magnesium oxide.
- An article as defined in claim 7 comprising a layer of metallic 4chromium superposed upon the topmost ceramic layer.
- An article comprising a metallic object yformed'of an alloy consisting essentially of iron and from about 10% to about 30% chromium, and a ceramic coating on said object said coating comprising a first layer in contact with said object of ceramic enamel substantially free of magnesium oxide and containing from about 2% to about 12% -ofchromium oxideand at least-one layer vof ceramic enamel superposed upon said first layer, said superposed 'layer containing at least about 10% of Amagnesium oxide.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Combustion & Propulsion (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Description
Dec. 21, 1954 A GAUDENZ] ETAL 2,697,670
CERAMIC COATED CHROMIUM STEEL Filed July 20, 1955 INV ENTORS ATTORNEY5 UnitedStates Patent O CERAMIC COATED CHROMIUM STEEL Arthur Gaudenzi, Wettingen, and Hannes Giger, Baden, Switzerland, assignors to Aktiengesellschaft Brown, Boveri & Cie., Baden, Switzerland Application July 20, 1953, Serial No. 369,188
Claims priority, application Switzerland `luly 28, 1952 11 Claims. (Cl. 117-70) This invention relates to ceramic-coated chromiumcontaining metallic objects and more particularly to structural parts such as turbine blades which are subject to thermal and mechanical stresses and to the corrosive action of hot gases containing corrosive materials such as vanadium compounds.
It is well known to coat thermally stressed metallic structural elements such as the exhaust pipes of internal combustion engines used on aircraft and the blades of gas turbines with protective layers of ceramic material. Such layers serve not only as heat insulation but also to protect the coated surface against corrosion and erosion by hot gases.
The use of fuel oil for the operation of gas turbines has given rise to the problem of protecting the turbine parts, particularly the blades against the attack of the corrosive slag formed when the oil is burned and particularly slag containing vanadium compounds. Vanadium compounds, when encountered under such conditions, prevent the formation of a protective oxide layer on steels and destroy existing oxide layers so that a progressive oxidation and erosion of steel structural parts such as combustion chamber walls and gas turbine blades which are contacted with combustion gases formed from vanadium containing fuel oils occurs.
It is known that magnesium oxide is strongly resistant to the attack of corrosive slags such as the vanadium containing slag derived from fuel oil. Chromium metal also provides a strongly resistant coating. But such protective coatings must adhere strongly to the parts to be protected and this is a problem in the case of the highly heat resistant chromium containing steels.
An object of the present invention therefore is to provide a strongly adherent and corrosion and erosion resistant coating for chromium containing steel objects and particularly a coating which will withstand the action of vanadium containing slags such as those produced by the combustion of fuel oil.
We have solved this problem in the following manner. First we apply a coating of a chromium oxide containing enamel. Such a coating is not particularly resistant to erosion but it has the merit of strong adhesion to the chromium steel surface and the further merit of strong adhesion to a superposed coating or coatings which are resistant to erosion. We then apply successive coatings of magnesia containing enamels, each successive coating having a larger content of magnesia until the desired thickness of coating and the desired magnesia content is attained. And finally we may apply a layer of chromium metal which is strongly adherent to the magnesia-containing layer. The resulting composite protective coating either with or without the chromium layer has a high heat conductivity and good stability under fluctuating temperature.
By chromium containing steel we mean alloys of chromium with iron containing about 14-30% of chromium and not more than about 0.5% of impurities such as carbon, silicon, manganese, sulfur, phosphorus etc.
The initial chromium oxide enamel layer should have a heat expansion which is less than that of the chromium steel. For example for use on a chromium steel containing to 30% of chromium and having a coefficient of expansion a=9.5-l2 l06 the enamel may have a coeicient of expansion a=8l0 l05. Thus after the enamel has been burned onto the steel surface and the product is cooled the steel shrinks more than the enamel and the latter is put under pressure and is much less likely to break than if it were put under tension. The difference should not however be too large as in the case of chromium-nickel steel (18% Cr and 8% Ni) which has a coecient of expansion a=18 l06. The chromium oxide enamel is burned onto the surface of the steel and the superposed layers of magnesia containing enamel are each burned onto the preceding layer.
The invention is illustrated in the accompanying drawings in which:
Fig. l is a diagrammatic section of a protective coating built up entirely of ceramic materials and Fig. 2 is a diagrammatic section of a coating comprising a metallic chromium top layer.
The coating of Fig. l is formed as follows: A coating layer 2 of chromium oxide enamel composition is applied to the surface of the body 1 of chromium steel having a chromium content of about 21%. This coating should have a heat expansion which is somewhat less than that of the body 1. A suitable chromium oxide enamel composition is the following, the parts being by weight. 4 parts of borax, 28 parts of feldspar, 23 parts of quartz, 5 parts of iiuorite, 15 parts of cryolite, 5 parts of soda and 4 parts of chromium oxide. The mixture is melted, cooled, pulverized, mixed with water sufcient to form a liquid coating, applied to the steel surface in any suitable manner as by brushing, spraying or dipping, dried and burned or baked at 850 C. to 900 C. for a few minutes. After cooling a layer 3 of the same enamel composition to which 10% to 20% by weight, based on the weight of the solid components, of magnesium oxide powder has been added is applied, dried and burned in the same way as the layer 2. Then layer 4 is applied, dried and burned,
said layer consisting of the original enamel composition to which 25 to 35% by Weight of magnesium oxide powder has been added. And finally layer o is applied dr1ed and A burned, said layer consisting ofthe original enamel composition with the addition of 40-60% by weight of magnesium oxide.
The layers of high magnesium oxide content provide excellent protection of the steel surface against vanadium containing slag. The layers adhere well to each other and the base layer 2 adheres well to the steel so that the entire multi-layer coating does not peel or crack even when subjected to sharp temperature changes. Obviously any desired number of layers may be applied and the magnesium oxide content may be increased to the desired extent by increasing the additions of magnesium oxide to the composition of the rst layer. The coating generally is built up to a thickness of at least l mm. and the thickness of the layers and the number thereof may be varied accordingly. It is desirable to increase the magnesia content of the layers by relatively small increments as illustrated but this is not essential as will appear from the following example.
Referring to Fig. 2, a layer 2 of the chromium oxide enamel composition described in connection with Fig. 1 is first applied to the chromium steel base 1 and baked. Then a layer 3 of said enamel to which preferably 40 to 60% by weight of magnesium oxide has been added is applied and baked. In effect layers 3 and 4 of Fig. l are omitted. Then the chromium layer 6 is applied by sprinkling metallic chromium in `powdered form onto the layer 3 while it is at a bright red heat. This results in the chromium being incorporated into the surface of and bonded to the ceramic layer. The resulting coating is particularly advantageous for use in turbine blades.
The above described coating formed by sprinkling chromium powder upon the hot ceramic layer of ceramic material may be reinforced by electroplating it with chromium. The chromium covering layer may be polished leaving the sharp edges in the case of turbine blades, intact. Due to the heat insulating action of the ceramic layer the temperature attained by the metal base of a turbine blade provided with a ceramic coating will be somewhat lower than an unprotected blade subjected to the same gas temperature.
The ceramic protective coating described above practically eliminates the attack of vanadium containing slags such as are derived from fuel oil. This greatly lengthens the life of combustion chamber walls and other structural parts which are exposed to such slags.
The invention is not limited to the particular enamel 'compositions vdescribed above. The base for vthe chromium oxide containing enamel may be any good enamel suitable for use on unalloyed steel. Many such enamels are well -known. Examples of such enamels Aare the following, the parts being :by weight.
Parts Parts (a) Borax 43.8 Sodium nitrate 2.0 Feldspar 27.7 Potassium oxide 0.3 Quartz 27.8 Manganese oxide 0.4 Fluorspar 2.9 Nickel-oxide 1.0 ASoda 8.8 Clay 11.6 (b') Borax 24.2 Cryolite 17.0 Feldspar .28.5 Potassium nitrate 5.0 Quartz v28.4 oda 5.7 4l-iluorspar `5. Kaolin 2.1
The chromium oxide content ofthe enamel may vary within the range from 212%.
We-claim:
1. An article comprising a metallic object formed of an alloy consisting essentially of iron and from about 14% to about 30% of chromium, anda ceramic'coating on said object said coating comprising a first layer in contact with said object of ceramic enamel substantially free of magnesium oxide and containing from about 2% to `about 12% of chromium oxide land at least one layer .of ceramic enamel superposed upon said -first layer, said superposed layer containing at least about of magnesium oxide.
2. An article as defined in claim 1 in which the superposed layer of ceramic enamel consists of a mixture of ctlhe composition of the first layer with magnesium oxi e.
3. .An article as defined in claim l in which the first layer contains about 4 parts of chromium oxide to 100 parts of other solids.
-4. An-article as defined in claim l in which the first layer is the product formed byheating to about850900 C. a mixture of finely divided borax, -feldspan quartz, fiuorite, cryolite, soda and chromium oxide.
5. An article as defined in claim l in which the first 'layer has a coefficient of expansion less than that of the metallic object. l
6. An article as defined in claim 1 in which the coating has a top layer of metallic chromium.
7. An article as defined in claim 1 in which the first layer is burned onto the surface of the metallic object and the coating comprises a plurality of superposed ceramic layers, each successive superposed layer containing more magnesium oxide than the layer below it and being burned onto the layer below it, the topmost of said ceramic layers containing at least about 30% by weight of magnesium oxide.
8. An article as defined in claim 7 comprising a layer of metallic 4chromium superposed upon the topmost ceramic layer.
9. An article as defined in claim 8 in which said chromium layer comprises finely divided chromium fused -intothe surface of the ceramic layer.
10. An article as defined in claim 8 in which said lchromium `layer is an `electro deposit vof fchromium.
111. An article comprising a metallic object yformed'of an alloy consisting essentially of iron and from about 10% to about 30% chromium, and a ceramic coating on said object said coating comprising a first layer in contact with said object of ceramic enamel substantially free of magnesium oxide and containing from about 2% to about 12% -ofchromium oxideand at least-one layer vof ceramic enamel superposed upon said first layer, said superposed 'layer containing at least about 10% of Amagnesium oxide.
ReferencesCited in the file of this patent Moore et al., National Advisory Committee for Aeronautics, Technical Note 2380, pp. 1-14 (1951). (Copy in Science Library.)
Harrison, American Society for testing Materials, Symposium on Corrosion of Materials at Elevated Temperatures, Special Technical Publication No. 108 (1950), pp. 114-121. (Copy in Science library.)
Claims (1)
1. AN ARTICLE COMPRISING A METALLIC OBJECT FORMED OF AN ALLOY CONSISTING ESSENTIALLY OF IRON AND FROM ABOUT 14% TO ABOUT 30% OF CHROMIUM, AND A CERAMIC COATING ON SAID OBJECT SAID COATING COMPRISING A FIRST LAYER IN CONTACT WITH SAID OBJECT OF CERAMIC ENAMEL SUBSTANTIALLY FREE OF MAGNESIUM OXIDE AND CONTAINING FROM ABOUT 2% TO ABOUT 12% OF CHROMIUM OXIDE AND AT LEAST ONE LAYER OF CERAMIC ENAMEL SUPERPOSED UPON SAID FIRST LAYER, SAID SUPERPOSED LAYER CONTAINING AT LEAST ABOUT 10% OF MAGNESIUM OXIDE.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH308578T | 1952-07-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2697670A true US2697670A (en) | 1954-12-21 |
Family
ID=4531882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US369188A Expired - Lifetime US2697670A (en) | 1952-07-28 | 1953-07-20 | Ceramic coated chromium steel |
Country Status (5)
Country | Link |
---|---|
US (1) | US2697670A (en) |
CH (1) | CH308578A (en) |
DE (1) | DE926707C (en) |
FR (1) | FR1081489A (en) |
GB (1) | GB725503A (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2823139A (en) * | 1952-05-23 | 1958-02-11 | Ver Deutsche Metallwerke Ag | Method of increasing the scaling resistance of metallic objects |
US2861010A (en) * | 1956-05-15 | 1958-11-18 | Gerald J Axelrod | Method of bonding porcelain to gold castings and articles resulting therefrom |
US2903375A (en) * | 1956-08-08 | 1959-09-08 | Renault | Method of coating a mould for use in a foundry |
US3031331A (en) * | 1959-10-23 | 1962-04-24 | Jr William L Aves | Metal-ceramic laminated skin surface |
US3034971A (en) * | 1958-09-09 | 1962-05-15 | Gen Electric | Process for producing an electrically insulated conductor |
US3054694A (en) * | 1959-10-23 | 1962-09-18 | Jr William L Aves | Metal-ceramic laminated coating and process for making the same |
US3173195A (en) * | 1957-02-19 | 1965-03-16 | Jerome H Lemelson | Method of making ducted panelling |
US3247383A (en) * | 1960-04-05 | 1966-04-19 | Minnesota Mining & Mfg | Infra-red reflector assembly for thermographic copying machine |
US3247428A (en) * | 1961-09-29 | 1966-04-19 | Ibm | Coated objects and methods of providing the protective coverings therefor |
US3280448A (en) * | 1961-11-02 | 1966-10-25 | Zenith Radio Corp | Process for fabricating miniature capacitors |
US3975165A (en) * | 1973-12-26 | 1976-08-17 | Union Carbide Corporation | Graded metal-to-ceramic structure for high temperature abradable seal applications and a method of producing said |
US20060026952A1 (en) * | 2004-08-06 | 2006-02-09 | Yamaha Hatsudoki Kabushiki Kaisha | Engine part |
EP1420144A3 (en) * | 2002-11-15 | 2009-02-18 | Rolls-Royce Plc | Method of protecting a vibration damping coating from foreign object damage |
DE102016202027A1 (en) * | 2016-02-11 | 2017-08-17 | Siemens Aktiengesellschaft | Impeller for a turbomachine |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE976381C (en) * | 1952-10-29 | 1963-07-25 | Brown Ag | Process for producing a protective layer on thermally highly stressed, scale-resistant metal parts |
JPS59120704A (en) * | 1982-12-27 | 1984-07-12 | Toshiba Corp | Heat resistant wall body against superhigh temperature |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE639922C (en) * | 1935-06-01 | 1936-12-16 | Pfaudler Werke Ag | Basic frit used to produce heat-resistant coatings |
-
1952
- 1952-07-28 CH CH308578D patent/CH308578A/en unknown
- 1952-08-09 DE DEA16327A patent/DE926707C/en not_active Expired
-
1953
- 1953-07-20 US US369188A patent/US2697670A/en not_active Expired - Lifetime
- 1953-07-21 FR FR1081489D patent/FR1081489A/en not_active Expired
- 1953-07-28 GB GB20875/53A patent/GB725503A/en not_active Expired
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2823139A (en) * | 1952-05-23 | 1958-02-11 | Ver Deutsche Metallwerke Ag | Method of increasing the scaling resistance of metallic objects |
US2861010A (en) * | 1956-05-15 | 1958-11-18 | Gerald J Axelrod | Method of bonding porcelain to gold castings and articles resulting therefrom |
US2903375A (en) * | 1956-08-08 | 1959-09-08 | Renault | Method of coating a mould for use in a foundry |
US3173195A (en) * | 1957-02-19 | 1965-03-16 | Jerome H Lemelson | Method of making ducted panelling |
US3034971A (en) * | 1958-09-09 | 1962-05-15 | Gen Electric | Process for producing an electrically insulated conductor |
US3031331A (en) * | 1959-10-23 | 1962-04-24 | Jr William L Aves | Metal-ceramic laminated skin surface |
US3054694A (en) * | 1959-10-23 | 1962-09-18 | Jr William L Aves | Metal-ceramic laminated coating and process for making the same |
US3247383A (en) * | 1960-04-05 | 1966-04-19 | Minnesota Mining & Mfg | Infra-red reflector assembly for thermographic copying machine |
US3247428A (en) * | 1961-09-29 | 1966-04-19 | Ibm | Coated objects and methods of providing the protective coverings therefor |
US3280448A (en) * | 1961-11-02 | 1966-10-25 | Zenith Radio Corp | Process for fabricating miniature capacitors |
US3975165A (en) * | 1973-12-26 | 1976-08-17 | Union Carbide Corporation | Graded metal-to-ceramic structure for high temperature abradable seal applications and a method of producing said |
EP1420144A3 (en) * | 2002-11-15 | 2009-02-18 | Rolls-Royce Plc | Method of protecting a vibration damping coating from foreign object damage |
US20060026952A1 (en) * | 2004-08-06 | 2006-02-09 | Yamaha Hatsudoki Kabushiki Kaisha | Engine part |
US7726121B2 (en) * | 2004-08-06 | 2010-06-01 | Yamaha Hatsudoki Kabushiki Kaisha | Engine part |
DE102016202027A1 (en) * | 2016-02-11 | 2017-08-17 | Siemens Aktiengesellschaft | Impeller for a turbomachine |
Also Published As
Publication number | Publication date |
---|---|
FR1081489A (en) | 1954-12-20 |
DE926707C (en) | 1955-04-21 |
GB725503A (en) | 1955-03-02 |
CH308578A (en) | 1955-07-31 |
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