Disclosed herein is a method of marking ceramic matrix composite articles. More specifically disclosed herein is a method that details the durable marking of ceramic matrix composite articles. Disclosed herein too are articles manufactured from the process.
Manufactured parts are often marked with identifying symbols, codes or numerals so that they can be easily identified for further use. Markings facilitate ease of inventory control as parts bearing an identical marking can be stored in common locations. In addition, marking of parts prevents accidental use of parts on the wrong assembly line or on the wrong article of commerce. Accurate marking of manufactured parts therefore plays an important role in commerce by facilitating speed of storage, assembly and maintenance of articles of commerce.
Ceramic matrix composites (CMCs) are used in a wide variety of high temperature, high stress, high performance applications such as in power generation turbines, aircraft engine turbines, and the like. These composites are particularly useful because of their high temperature capabilities and light weight. Ceramic matrix composites are manufactured by infiltrating a preform with a matrix material to form the matrix.
Marking of CMCs poses challenges that marking of metals does not. Traditional approaches for marking metal parts can include mechanical methods like dot peening which would cause damage to a CMC because of the brittle surfaces of CMCs. Additionally, the higher temperature environments for using CMCs (such as in turbines) relative to most metal parts causes challenges when ink and pencil marking is used. Ink and pencil formulations are generally not formulated to withstand these higher temperature conditions.
It is therefore desirable to devise methods and compositions that can be used for marking CMCs, which can withstand extended durations at high temperatures in unfavorable environments.
In one aspect, an article comprises a substrate that comprises a ceramic matrix composite; and a metal oxide layer disposed on the substrate; where the metal oxide layer has a marking etched into the metal oxide via laser ablation. The markings include alphabets, numbers, symbols, bar codes, matrix bar codes, quick response codes, or a combination thereof.
In one embodiment, the article comprising a bond coat disposed between the substrate and the metal oxide layer.
In another embodiment, the metal oxide layer is directly in contact with the substrate.
In another embodiment, the ceramic matrix composite comprises fibers that comprise silicon carbide, oxide ceramics and carbon and wherein the fibers are embedded in a matrix that comprises SiC, Al2O3, BN, B4C, Si3N4, MoSi2, SiO2, SiOC, SiNC SiONC, ZrC, HfC, or a combination thereof.
In another embodiment, the ceramic matrix composite has a different refractive index from the metal oxide layer.
In another embodiment, the ceramic matrix composite has a different reflectivity from the metal oxide layer.
In another embodiment, the metal oxide layer comprises a silicate, a perovskite and/or a rare earth metal oxide.
In another embodiment, the rare earth metal oxide has a diffuse reflectivity for incident light with wavelength between 400 and 700 nm that is two times greater than the diffuse reflectivity of SiC/SiC ceramic matrix composite.
In another embodiment, the metal oxide layer is ablated through at least 95% entire thickness.
In another embodiment, the metal oxide layer is ablated through at least 99% entire thickness.
In another embodiment, the metal oxide layer is ablated through its entire thickness.
In another embodiment, the bond coat layer is ablated through a portion of its thickness.
In another embodiment, a difference between the reflectivity of the CMC substrate and the metal oxide layer facilitates identification of the markings.
In another embodiment, a difference in refractive index between the metal oxide and the CMC substrate results in reflection in incident light, which is used to identify the marking.
Disclosed herein too is a method comprising disposing upon a ceramic matrix composite a metal oxide layer; and laser ablating the metal oxide layer to etch the metal oxide layer. The etchings produce markings that comprise alphabets, numbers, symbols, bar codes, matrix bar codes, quick response codes, or a combination thereof.
In an embodiment, a bond coat is disposed between the ceramic matrix composite and the metal oxide layer.
In another embodiment, the metal oxide layer is ablated through its entire thickness.
In another embodiment, the metal oxide layer is ablated through a portion of its entire thickness.
Disclosed herein too is a method of identifying an article comprising illuminating the article with an incident beam of light; where the article comprises a substrate that comprises a ceramic matrix composite; and a metal oxide layer disposed on the substrate. The metal oxide layer has a marking etched into the metal oxide via laser ablation. The marking includes alphabets, numbers, symbols, bar codes, matrix bar codes, quick response codes, or a combination thereof. Reflected light from the article is used to identify the article.
In an embodiment, the incident beam comprises non-coherent light or a laser.
Disclosed herein is a method of marking a ceramic matrix composite comprising disposing upon a stencil having a pattern on a ceramic matrix composite and disposing a slurry that comprises a metal oxide on the stencil. The slurry covers the pattern. The slurry is cured. The stencil is removed. The slurry left behind after stencil removal is heat treated to produce a metal oxide layer that identifies the ceramic matrix composite. The marking comprises alphabets, numbers, symbols, bar codes, matrix bar codes, quick response codes, or a combination thereof.
Disclosed herein are articles that have disposed on them a suitable composition that can be marked for purposes of identification. The composition includes a multilayered composite that comprises a metal oxide layer on a CMC substrate, where the metal oxide layer has a different refractive index from that of the matrix used in the CMC substrate. When regions of the metal oxide are removed via laser ablation, the difference in refractive indices between the remaining regions of metal oxide and the exposed regions of CMC surface creates a pattern with sufficient contrast between the markings and their surroundings that facilitate recognition even after extended periods of time at elevated temperatures. In addition, reflections of light from the markings also facilitate identification and recognition after extended periods of time at elevated temperatures. In an embodiment, the markings can be deciphered because of an optical contrast created due to the difference in light reflected from the metal oxide versus that reflected from the matrix material used in the CMC.
The composition and the marking made thereon can withstand adverse conditions (e.g., high temperature, high energy electromagnetic radiation, and the like) during manufacturing and during use (e.g., high temperatures, high stresses, corrosive environments, and the like) for extended periods of time. This ability to withstand a high temperature, high energy marking process followed by survival in adverse conditions for extended periods facilitates ease of storage, maintenance and replacement of such marked parts when needed.
Disclosed herein too is a method of marking the article using laser ablation. The method comprises disposing a layer of a metal oxide on the CMC surface such that the reflectivity of the metal oxide is different from the reflectivity of the CMC. In an embodiment, the reflectivity of the metal oxide is different from the reflectivity of the matrix used in the CMC. The metal oxide is preferably one that has a greater reflectivity from that of the matrix material used in the CMC, such as, for example, a rare earth oxide. In an embodiment, the metal oxide has a diffuse reflectivity for incident light with wavelengths between 400 and 700 nm that is at least two times greater than the diffuse reflectivity of the matrix used in the ceramic matrix composite.
In another embodiment, the metal oxide is a rare earth metal oxide that has a diffuse reflectivity for incident light with wavelength between 400 and 700 nm that is at least two times greater than the diffuse reflectivity of the matrix used in the ceramic matrix composite. Upon ablating the rare earth metal oxide with a laser, an optical contrast is created due to the difference in light reflected from the metal oxide versus that reflected from the matrix material used in the CMC. This optical contrast facilitates identifying the marking and hence the article.
Laser ablation methods have been used in the past to mark article surfaces. These methods have traditionally relied on changing the structure of the ceramic surface via ridges and valleys to create (light and dark) contrast. These micro-scale structures however, are prone to oxidation over time which can significantly reduce contrast. This makes the part identification difficult especially after extended periods of time when the marking has substantially disappeared. This problem can be alleviated by disposing a metal oxide on a CMC substrate, where the metal oxide has a substantially different refractive index from that of the matrix (and hence the CMC) and ablating the metal oxide down to the surface of the CMC. In one embodiment, a bond coat can be applied to the CMC surface and the metal oxide can be disposed on the bond coat. The laser ablation then may be used to ablate the metal oxide and a portion of the bond coat thereby preventing the CMC surface from damage.
Layered structures define a wide variety of construction arrangements, including lightweight laminated composite articles. Laminated composites typically are defined by a continuous, essentially planar array of continuous fibers embedded in a matrix defining a lamina or ply, a plurality of plies forming a laminate composite. These composite articles can be arranged to meet various in-plane stiffness or strength needs by appropriate stacking of similar orthotropic plies of dissimilar orientation. Ceramic matrix composites generally comprise fibers that comprise silicon carbide, oxide ceramics and carbon. Exemplary matrix materials include SiC, Al2O3, BN, B4C, Si3N4, MoSi2, SiO2, SiOC, SiNC SiONC, ZrC, HfC, or a combination thereof. An exemplary combination of fiber and matrix (in a CMC) is silicon carbide fibers and a silicon carbide matrix.
The refractive index for the CMC substrate 102 is different from the refractive index of the metal oxide layer 104. The refractive index can be measured in different wavelengths of the electromagnetic spectrum. For practical reasons however it is desirable that the refractive index of the CMC substrate 102 is different from the refractive index of the metal oxide layer in the visible region of the electromagnetic spectrum and in the infrared region of the electromagnetic spectrum. The refractive index of the CMC substrate can be lower or higher than the refractive index of the metal oxide layer.
The refractive index of the CMC composite or of the CMC matrix (the matrix material used in the CMC composite) can be about 1.4 to 4.0, preferably 1.44 to 3.2, preferably 1.5 to 3.0 in the visible region of electromagnetic radiation.
The metal oxide layer 104 is disposed directly on the CMC substrate 102 (see
The metal oxide can preferably undergo laser ablation without undergoing degradation or cracking. It is preferable for the metal oxide to not generate compounds that can degrade the CMC during the laser ablation process. For this reason, it is desirable to use metal oxides that are free from halogens, nitrates, sulfates, phosphates, or a combination thereof. The metal oxide layer 104 comprises a metal oxide that has a different refractive index from that of the CMC matrix.
Examples of metal oxides that may be used for the metal oxide layer include silicates, aluminates, titanates, zirconates, perovskites, rare earth metal oxides, and so forth that can bond with silicates, aluminates, and the like formed on the surface of the CMC composite.
Exemplary metal oxides include silicates, zirconates, titanates, aluminates, stannates, niobates, tantalates and rare earth oxides. Exemplary inorganic oxides include silica, aluminum oxide, silicon dioxide, calcium oxide, cerium oxide, copper oxide, titanium oxide, zinc oxide, zirconium oxide, tantalum oxide, niobium oxide, yttrium oxide, magnesium oxide, Mg2SiO4, MgO, CaTiO3, MgZrSrTiO6, MgTiO3, MgAl2O4, WO3, SnTiO4, ZrTiO4, CaSiO3, CaSnO3, CaWO4, CaZrO3, MgTa2O6, MgZrO3, MnO2, PbO, Bi2O3 and La2O3, CaZrO3, BaZrO3, SrZrO3, BaSnO3, CaSnO3, MgSnO3, Bi2O3/2SnO2, Nd2O3, Pr7O11, Yb2O3, Ho2O3, La2O3, MgNb2O6, SrNb2O6, BaNb2O6, MgTa2O6, BaTa2O6, Ta2O3, or the like, or a combination thereof. Exemplary metal oxides include Mg2SiO4, MgO, CaTiO3, MgZrSrTiO6, MgTiO3, MgAl2O4, MgTa2O6, MgZrO3, or the like, or a combination thereof.
Silicates are preferred. Silicates that may be used in the metal oxide layer are preferably from Group 2A of the Periodic Table, i.e., berrylium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra). Preferred metal silicates include Mg2SiO4, CaSiO3, BaSiO3 and SrSiO3. In addition to Group 2A metals, the present metal silicates may include metals from Group 1A, i.e., lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr). For example, metal silicates may include sodium silicates such as Na2SiO3 and NaSiO3-5H2O, lithium silicates such as LiAlSiO4, Li2SiO3 and Li4SiO4. Additional metal silicates may include Al2Si2O7, ZrSiO4, KAlSi3O8, NaAlSi3O8, CaAl2Si2O8, CaMgSi2O6, BaTiSi3O9, Zn2SiO4 or a combination thereof.
The rare-earth elements, also called the rare-earth metals or the lanthanides (yttrium and scandium are included as rare-earths) are a set of 17 nearly indistinguishable lustrous silvery-white soft heavy metals. Scandium and yttrium are considered rare-earth elements because they tend to occur in the same ore deposits as the lanthanides and exhibit similar chemical properties but have different electronic and magnetic properties. Rare earth oxides include oxides of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium, or a combination thereof.
The rare earth oxide has a refractive index that is different from that of the CMC. The rare earth oxides generally have refractive index values of 1.5 to 2.7, preferably 1.7 to 2.3 and more preferably 1.8 to 2.2. For example, La2O3 has a refractive index ranging from 1.85 to 1.95 with increasing thickness, Pr6O11 from 1.92 to 2.05, also with increasing thickness, and Nd2O3 with a value of refractive of n=2.05. Rare earth metal oxides are preferred for use in the metal oxide layer 104.
The metal oxide layer 104 is disposed on the CMC substrate 102 via a sol gel reaction, a slurry, or alternatively, the metal oxide layer 104 is preformed and disposed directly on the CMC substrate.
The metal oxide layer 104 may have a thickness of 0.025 to 0.8 millimeters, preferably 0.05 to 0.5 millimeters, preferably 0.1 to 0.4 millimeters.
The bond coat 106 is an optional layer and may be used on those occasions when it is desirable to protect the CMC composite 102 from the effects of laser ablation. The bond coat 106 is used to permit the laser ablation to remove a portion of the metal oxide layer 104 and a portion of the bond coat 106 without penetrating or disturbing the CMC substrate 102.
The bond coating 106 prevents the CMC substrate 102 from oxidation in a range of temperatures from room temperature to up to at least about 3000° F. (1650° C.) and greater. The bond coating is an exemplary protective coating that take advantages of glass materials having low melting point temperatures in combination with oxygen scavenging additives to achieve high mechanical and oxidation resistant properties suitable for the refractory based substrate.
A process for applying an oxidation resistant coating may comprise mixing at least about 10% by volume to up to about 99% by volume of at least one silica based material and at least about 1% by volume to up to about 90% by volume of at least one oxygen scavenger in a liquid medium to form a slurry. Suitable liquid media include water, alcohols, binders, terpineol, or a combination thereof.
The binders may be organic-based liquid media such as acrylic polymers, or alternatively, inorganic-based such as colloidal silica. Suitable mixing processes may include, but are not limited to, mechanical mixing techniques, manual mixing techniques, ultrasonics, cavitation, agitation, combinations comprising these techniques, and the like. For example, representative mechanical mixing techniques may include grinding, ball mixing, high energy milling (e.g., Spex), shear mixing, stirring, centrifugal mixing, combinations comprising at least one of the foregoing, and the like.
Suitable silica based materials may comprise silica, modified silica, and the like. Modified silica may comprise silica modified by other compounds or elements, for example, silicates such as sodium silicate, borosilicates, hafnium silicates, zirconium silicates, and mixtures thereof. These various silica based materials exhibit a viscosity of about 1×102 poise to about 1×107 poise in a temperature range of about 1,292° F. (700° C.) to about 3,272° F. (1,800° C.), possess a particle size range of about 150 mesh to about 325 mesh, and form a viscous glass phase material when heat treated that is suitable as a carrier for at least one oxygen scavenger. This viscosity range permits easier inclusion and dispersion of the oxygen scavengers throughout the silica based materials during the coating and heat treatment steps.
The oxidation resistant coating of the present invention provides oxidation resistance primarily by active reaction with oxygen rather than only providing a passive barrier to oxygen flow to an article's surface. As the coating(s) are exposed to oxidative operating conditions, the coating(s) erodes and exposes the oxygen scavenger additives. The oxygen scavengers oxidize to form non-gaseous oxidation products such as SiO2, Al2O3, B2O3, etc., which then add to and rebuild the coating. The glassy phase flows at elevated temperature to seal cracks and accommodate mismatches of the coefficient of thermal expansion of the various layers. As a result, the coating in turn resists spallation and cracking and instead relieves the stress caused by the formation of the non-gaseous oxidation products.
The oxygen scavenger may be an element or compound or multiphase component that reacts with oxygen to form a relatively stable, non volatile oxygen-containing compound or phase. Suitable oxygen scavengers may comprise silicides and/or borides of aluminum, molybdenum, tantalum, chromium, titanium, hafnium, zirconium, yttrium, mixtures thereof, and the like. In addition, other refractory metals, and other metals that form refractory oxides, silicates, borides, and mixtures thereof, known to one of ordinary skill in the art may also be utilized as suitable oxygen scavengers. The volume percent of the oxygen scavenger within the layers of coating may preferably be in the range of about 1% to about 90% by volume of the layers of coating, and more preferably in the range of about 5% to about 75% by volume of the layers of coating.
If desirable, a viscosity modifier may be added to the slurry in an amount sufficient to rheologically control the viscosity of the targeted glass phase(s). Suitable viscosity modifiers may include, but are not limited to refractory materials, metal oxides, mixed metal silicates, mixtures thereof, and the like. Optionally, a viscosity modifier additive may be added to the slurry to impart steam resistance to the article. In the alternative, the silica based material may also include, as part of its composition, the viscosity modifier additive. Suitable viscosity modifier additives may include mullite, alkaline earth aluminosilicates including barium strontium aluminosilicate (BSAS) and strontium aluminosilicate (SAS), yttrium silicates, rare earth silicates, hafnium or zirconium silicate, oxides of hafnium, zirconium, titanium, silicon, yttrium, rare earth metals, tantalum, niobium, aluminum and mixtures thereof, and the like. In addition, these viscosity modifier additives may also be used to impart additional steam resistance.
After disposing the slurry containing the bond coat 106 precursors to the CMC substrate 102, it is subjected to heat and pressure to evaporate the liquid components such as solvents and so on. Pressure may be used to facilitate bonding of the bond coat 106 to the CMC substrate 102. Following the formation of the optional bond coat 106, the metal oxide layer 104 is disposed on the bond coat 106 (if present) or directly on the CMC substrate 102. The metal oxide layer 104 is then heat treated to remove solvents (if applied in the form of sol gel solution) and/or to bond the metal oxide layer 104 to the bond coat 106 or to the CMC substrate 102. The CMC substrate 102 with the optional bond coat 106 and the metal oxide layer 104 disposed thereon is referred to herein as a multilayer composite. The multilayer composite is then subjected to laser ablation to create the marking that identifies the part.
The metal oxide layer 104 is then subjected to laser ablation to etch away a portion of the metal oxide layer to create the marking that identifies the part. In an embodiment, the metal oxide layer 104 is etched to the interface with the bond coat 106 or to the interface with the CMC substrate 102 when the bond coat 106 is not used. In another embodiment, the metal oxide layer 104 is etched below the interface of the metal oxide layer 104 with the bond coat 106 and into the portion of the bond coat 106. A portion of the bond coat above the surface of the CMC substrate 102 is left untouched, thus protecting the CMC substrate 102 from any adverse effects of the ablation.
These concepts are depicted in the
In one embodiment (not shown), the markings may be developed by ablating the metal oxide (and the bond coat-see
In another embodiment, in those regions where the metal oxide is contacted by the laser beam almost the entire height (i.e., the thickness) of the material is removed. In this embodiment, during the laser ablation of the metal oxide layer 104 it is desirable to leave the CMC substrate untouched by the laser beam. In other words, the thickness of the metal oxide layer is reduced almost to zero in those regions that are ablated while the surrounding metal oxide is left untouched. A very thin portion of the metal oxide layer 104 (less than 5% of the original thickness, preferably less than 1% of the original thickness) is still in contact with the CMC substrate 102 after the laser ablation. In an exemplary embodiment, the residual coating should be less than 1 micrometer. At 1 micrometer thickness or less, some incident light will transmit through the coating and reflect off of the underlying CMC, giving a different visual appearance, which is used to identify the marking.
In another embodiment, in some cases, a small amount (less than 50% of the coating thickness) is removed from the underlying CMC. The difference in refractive index between the metal oxide layer 104 and the CMC substrate 102 results in different amounts of light being reflected or scattered thus making the markings visible and consequently the component identifiable.
In
In
In an embodiment, in one method of reading the marking, a scanning device sends forth a beam of light (e.g., incoherent or laser) that interacts with the marking on the CMC part. A portion of the incident light is reflected back to the scanning device. A photodiode in the scanning device detects how much of the light is reflected back and this reflected light may be used to decipher the marking and identify the part.
This method is advantageous in that it protects the CMC substrate from degradation by the laser beam. The presence of a metal oxide layer as the source of the marking prevents further oxidation of the marking. In the past, oxidative degradation has caused the marking to disappear over time thus making the part unidentifiable.
The method described herein can be used to prepare a variety of components comprising matrix composites such as components in the aviation industry, marine industry and energy industry. Exemplary components include components for gas turbine engines, such as in high pressure compressors (HPC), fans, boosters, high pressure turbines (HPT), and low pressure turbines (LPT). More specifically exemplary components include combustion liners, shrouds, nozzles, stators, vanes, and blades.
While the invention has been described with reference to some embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
This application claims the benefit of U.S. Application No. 63/225,052, filed Jul. 23, 2021, the disclosure of which is incorporated herein by reference in its entirety.
Number | Date | Country | |
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63225052 | Jul 2021 | US |