TW201026897A - Protective coating and method - Google Patents

Abstract

A device comprising (i) a first layer having a first surface comprising a first metal; and (ii) a second layer comprising an oxide of a second metal bonding directly to the first surface of the first layer and covering at least a part of the first surface of the first layer, wherein: (A) the interface between the first layer and the second layer is substantially dense and has an irregular topography; and (B) the second metal is capable of forming an alloy with the first metal when the second metal is deposited on the first surface of the first metal at an elevated temperature. The device can be advantageously formed by a process including a step of forming a mixture such as an intermetallic of the first metal and the second metal over the first metal, followed by oxidation of the metal mixture at an elevated temperature.

Description

201026897 VI. Description of the invention: [Technical field to which the invention pertains] This description relates to protective coatings and methods for metals. In particular, the present invention relates to oxide protective coatings for precious metals and methods of forming such coatings. The present invention is useful for the purification protection of platinum elements in glass delivery systems at elevated temperatures of oxidizing air. '[Prior Art] ^ Recently, attention has been focused on reducing the development of component damage methods and components, which may occur in harsh thermal environments such as high temperatures that may cause or accelerate degradation of the primary processing components. The damage of such processing elements is costly and can easily cause other hidden processing problems. An example of a process performed in a harsh thermal environment is glass production processing, such as U.S. Patent No. 3,338,696 (Dockerty) and U.S. Patent No. 3,682,609 (Dockerty). While many glass processing units are made of durable, inert materials such as precious metals, high processing temperatures can create harsh environments, and as a result, components can be subject to oxidation and thermal stress. For example, the glass of an electronic display can be handled, transported, and formed using precious metals. Temperatures such as those used in glass processing techniques are high enough to produce volatile volatility on the bare surface of oxygen-rich metal parts. Metals are then reduced to form metal particles. During this treatment, it is possible to produce inclusion contaminants of the reduced metal particles in the glass. The limits of this contaminant may be low, especially for semiconductor applications where high glass ΐ (smoothness, homogeneity, etc.) is required. There is therefore a need to address the previously mentioned objects and the shortcomings associated with conventional glass manufacturing 201026897 and other processing. These and other needs are met by the components and methods of the present invention. [Brief Content] Each item may be illustrated by one or more embodiments, and may include one or more specific embodiments. It should be understood that the embodiments may or may not overlap each other. Thus, an embodiment or a portion of a particular embodiment thereof may or may not fall within the scope of another or particular embodiments thereof, and vice versa

The first related device of the invention includes: (1) having a first layer comprising a first metal first surface; and (i) a second layer comprising a second metal oxide directly bonding to the first layer a τ surface, and covering at least a first layer - a table - at least a portion, wherein the first layer and the second layer are substantially dense and have an irregular shape; and (Β) When the second metal is deposited on the first surface % of the first metal at elevated temperatures, the second metal may form an alloy with the first metal. j In a particular embodiment of the invention of item - (6) by the second metal and - The metal mixture _ part metal _, the thickness is the second layer supported by the real f plate, when the thin _- a major surface is exposed to the time of the base metal in the air, the temperature of the county is the film. Forming a dense oxide on an inert substrate In a particular implementation of the first aspect of the invention, the first metal contains the genus 4 201026897 and the second metal contains at least one of Ai, zr and & In a particular embodiment, the first layer comprises Pt· and the second layer consists essentially of Al 2〇3。 In a particular embodiment of the first aspect of the invention, the interface between the first layer and the second layer has a laminated refractive index of at least 15 (), in a particular embodiment k is less than 1 60' At least h 65 in the embodiment, in a particular embodiment, at least in the particular embodiment of the invention, the second layer has a thickness of from 2 m to 8 G, in the particular real towel, the m-micron, in the special = In other embodiments, from 20 micrometers to 6 micrometers, in certain other embodiments, from 25 micrometers to 45 micrometers, it is destined to be from 30 micrometers to 40 micrometers. The specific embodiment of the first embodiment of the present invention is dissolved. Component of the transport system. The apparatus is a glass melting system which is a stirred tank. In the particular embodiment of the invention, the clarifier tube of the system is in the specific embodiment of the invention. The molten glass is subjected to shear stress. In a specific embodiment of the first embodiment of the present invention, the towel device is a cover of the cake, and the device is a flange, for example, a conductive flange for transmitting electric power. In a particular embodiment of the first aspect of the invention, the second layer covers substantially ^ All outer silk surfaces, the butterfly ride secrets the atmosphere containing the gas. 201026897 The two layers are substantially opposite to the second layer. The second layer is substantially free of the first metal in the specific embodiment of the first item of the present invention. An oxide such as Pt 〇 2 is impermeable. In a particular embodiment of the invention, it is first impermeable. In a particular embodiment of the invention: - the second metal in the gold 4 state ©

In the first embodiment of the present invention, the second layer and the feature of mutual locking are formed at the interface thereof. - The acoustical term is a method of exposing the exposure to the temperature of the first metal in the protective device. The method comprises the following steps: (a) at least the first surface of the first metal Providing a precursor layer comprising a genus, the second metal may form an alloy with the first metal in the case where the precursor layer is provided; and (b) in the Wei air at the elevated temperature Forming a second layer of germanium containing a second metal oxide. In a particular embodiment of the second aspect of the invention, the first layer comprises pt. > In the second meal of the Bhagada, the first layer contains pt, and the second metal contains at least one type of Al si and society. In a particular embodiment of the second aspect of the invention, the precursor layer has a thickness of from 7 micrometers to i2G micrometers in step (a), from 1 () micrometers to (10) micrometers in a particular private shot, and 15 in certain other embodiments. Micrometers to 8 Å micrometers in particular, in embodiments 20 micrometers i 60 micrometers, in certain other embodiments 20 micrometers to 50 micrometers, in certain other embodiments 25 micrometers to 45 micrometers, 6 201026897 in particular In other embodiments, it is from 3Q microns to 4Q microns. In the present invention, in the second embodiment of the second aspect of the present invention, in the specific embodiment of the second aspect of the present invention, the first step is formed in the step (b): = the interface between the first and second layers has a combined second rate = •, in a particular embodiment at least 1.55, in a particular embodiment at least 1, in a particular embodiment at least from 65, in a particular embodiment It is at least 1.70, and in a particular embodiment at least 175. In a particular embodiment of the second aspect of the invention, at least one of the at least three chemical vapor deposition coated powder bath squirts is included in step (a), in a particular embodiment of the second aspect of the invention, the steps (b) is carried out in a preheating step. / In a particular embodiment of the second aspect of the invention, step (b) is performed in situ when the apparatus is installed in the operating system. In a particular embodiment, the operating system is a glass glaze and/or transmission system. In a particular embodiment of the second aspect of the invention, at the end of step (6), the second layer has a thickness of from 5 micrometers to (9) micrometers, and in particular embodiments from 1 micrometer to 70 micrometers, in certain other embodiments 2 microns to 6 microns, in certain other embodiments 20 microns to 50 microns, and in certain other embodiments 30 microns to 40 microns. In a particular embodiment of the second aspect of the invention, in step (a), the precursor layer is provided substantially comprising a mixture of a first metal and a second metal. 201026897 In a particular embodiment of the second aspect of the invention, the temperature is raised at the end of step (b) as a measure of the melting temperature of the IGGiTC to the precursor layer. In a particular embodiment of the second aspect of the invention, in step (6), the second metal is completely converted to its oxide in the first layer.

In a particular embodiment of the second aspect of the invention, in step (b), the precursor layer is heated to an elevated temperature which increases the temperature rate such that the second metal oxidizes without significant flow of molten second metal at the first metal on. The third aspect of the present invention relates to the process of making a glass sheet, which is carried out by using the apparatus described in the above description and will be described in detail below. In a particular embodiment of the third aspect of the invention, the apparatus comprises a stirred tank, a clarifier, a flange, or a connecting tubular member. Embodiments of one or more of the present invention have one or more of the following advantages. First, a dense, fire resistant protective coating can be formed on the outer surface of the metal structure to protect against harmful oxidation. Second, the coating film can be formed on a surface having a complicated shape. Third, the coating can be formed at a relatively low cost. Fourth, the coating has an interface bonding strength between the first metal layer and the second metal oxide protective layer. The other embodiments of the invention are disclosed in the Detailed Description of the Drawings. The prior general description and the following detailed description are to be considered as illustrative and illustrative and not restrictive. [Embodiment] g 201026897 The present invention will be immediately understood by the following detailed description, drawings, examples, and claims. However, it is understood that the present invention is not limited to the specific components, objects, devices and methods disclosed, unless otherwise stated. Change it. It is also understood that the terms used herein are used merely to describe a particular item and are not intended to be limiting. In the specification and the scope of the patent application, the terms used are defined as follows: In the specification and the scope of the patent application, the singular articles "a","an" and "the" also include the meaning of the plural unless It is also clearly stated. For example, "ingredients" include the two or more of the ingredients, etc. The range can be expressed as a specific value and/or to "about" another specific value. When expressed in the range, An item consists of a particular value and/or to another particular value. Similarly, when the value is expressed as an approximation by the preceding plus, it is understood that the particular value forms the other. It is further understood that each endpoint value of each range represents a relationship with another endpoint and is not governed by the other endpoint. For example, if a particular metal component is revealed and described, and some changes are made to the metal composition, it will be considered that each combination and arrangement of metal components is possible unless otherwise stated. Therefore, if the components A B, and c 201026897 types and the components D, E, and F types and the combination A-D are revealed, then each

Individual and common situations will be considered. That is, in this example each combination AE, AF, BD, BE, BF, CD, CE, and CF are explicitly considered and should be considered by A, B and C; D, E and F, and the combination of examples AD reveals Out. Similarly, the concept is also applicable to the various aspects of the invention, including the non-limiting steps of making and using the disclosed components. Thus, if there are additional steps that can be implemented, it is understood that each of these additional steps can be implemented in any particular embodiment or combination of embodiments of the disclosed methods, and that each of these combinations are specifically contemplated and considered It has been revealed. As used herein, "% by weight" or "% by weight" unless otherwise indicated is the ratio of the weight of the component to the total weight of the components comprising the components. Percentage of the refractive index used herein. The term is used to describe the shape of the first layer of material and the second interlayer of the material. The refractive index of the laminate ((1) is defined as follows: Cl = Lc/Ls' where Lc is the length of the curved line segment at two points on the joint interface, The interface wear distance from a plane substantially perpendicular to the central plane of the first layer of material is measured at a resolution of about 1 egg; and Ls is the length of a straight segment connecting the same two points. The gauge for measuring the refractive index of the laminate will be TF details. Therefore, a perfect flat interface will make CI =1, and the higher the α, the more irregular the shape of the interface. It should be understood that the resolution of the measurement may affect the final U value and thus the target: CI is measured at an approximate resolution. The shape π of the irregularity of 201026897 means that the laminated refractive index of the interface is at least 1.48. The higher the ci value, the larger the contact area between the first layer and the second layer, so the first layer And second The stronger the adhesion between the two. As used herein, a substantially dense interface means that the interface is substantially free of voids when viewed at a resolution of 1/m. * I. Apparatus of the invention: The device of the present invention comprises: (i) a first layer having a first surface comprising a first metal; and (1) a second layer comprising a second metal oxide directly bonded to the first surface of the first layer, and Covering at least the surface of the first layer to:, wherein: (A) the interface between the first layer and the second layer is truly dense and has an irregular shape; and (8) when the second metal is raised At a temperature, deposited in the first metal (four) - table, the second metal may form an alloy with the first metal. In a particular embodiment, the first metal and the second metal are more advanced to meet the following conditions: (6) comprising a -metal and The thin metal thickness of the second metal is substantially equal to the second layer of the inert substrate supported by the 'main surface' exposed to the air, and the temperature between the 诵.c and the first degree is increased. The second metal can be oxidized and formed on an inert substrate Real oxide film. The invention can be a stand-alone device or a large system ☆ P-knife so that the device can be a fluid or a reaction medium. In addition to the two layers indicated above, the device can further comprise Adjacent to the first 201026897 or another layer of the first layer. For example, the device may include a third layer adjacent to the second layer covering at least a portion of the second layer. Further, for example, the device may further include an upper layer adjacent to the first layer. The second surface covers at least a fourth layer of the first layer of the second sheet. The apparatus may further comprise other functional elements separate from the first and second layers. In one embodiment, the apparatus of the present invention comprises a carrier such as glass melt. A high temperature fluid conduit comprising a wall made of a first metal covered by a second layer of a second metal oxide. Such a conduit may be a clarifier between the glass melting and transporting different stations of the race, or a connecting pipe or the like. In another embodiment, the apparatus of the present invention comprises a high temperature fluid such as a glass melt, a vessel in which the mixing and homogenization is imparted. In embodiments in which the apparatus is operated at elevated temperatures, such as the apparatus for treating glass fluids as discussed above, the first metal preferably comprises a precious metal. Precious metals are known for their resistance to enthalpy and resist oxidation and corrosion of materials such as glass fluids. Thus, on the reverse side of the first surface of the first layer, the first layer of the apparatus of the present invention can be used to contact the high temperature fluids treated by the apparatus. For example, the apparatus includes a clarifier for treating a glass fluid, and the wall of the clarifier may be composed of a pt or a rib test piece, the inner surface may contain glass melt during normal operation, and the outer surface may be covered with an Ah 〇 3 coating. Therefore, the first layer may be composed of a metal or a combination of metals. However, precious metals are usually very expensive, so the first layer is preferably as thin as 12 201026897. In addition, even precious metals like Pt and Rh are easily oxidized at temperatures above 500 C, which are via the following reactions:

Pt (solid) + 〇 2 (gas) <-> Pt 〇 2 (gas) 〇)

Rh (solid) + 〇 2 (gas) > Rh 〇 2 (gas) (2) Oxidation causes loss of metal, thinning of metal siding, and loss of Pt in the glass melt, which is due to pt〇2 Subsequent dissociation of the gas and condensation of Pt particles on the cooler surface are very undesirable phenomena. The second layer of the second metal oxide of the apparatus of the present invention can be used to inhibit the diffusion of ruthenium 2 from the air to the exposed device, thereby inhibiting the above reaction formula (1), even at elevated temperatures such as glass clarifiers: The normal operating temperature may exceed ^卯^. When the two metals can be contacted at an elevated temperature, such as 5 〇〇ΐ or more, the second metal of the metal 爿i state can be alloyed with the first metal in the metallic state. The ability to alloy can result in a staggered and stacked interface between the first and second layers of the apparatus of the present invention. It should be noted that as described above, the alloy may be a mixture or combination of two metals of different molar percentages. Indeed, under the established alloying conditions, the first metal and the second metal can form alloys of various types. For example, when the two metals are in contact with each other at a lifting temperature of, e.g., 800 < t, the second metal may be Pt, and may form an alloy with the various components of the second metal represented by PtxAly. Further, as described above, the first layer may contain a combination of a plurality of metals (e.g., Pt-Rh test pieces). In this case, in addition to the first metal (e.g., Pt), the other metal included in the first layer 13 201026897 can form an alloy with the second metal at elevated temperatures, which is not so required in the present invention. The second layer comprising the second metal oxide covers at least a portion of the first surface of the at least first layer and at least partially separates the portion of the first layer first surface from the environment to be exposed, such as in the first layer Under the condition, the first surface of the first layer is a reactive atmosphere, for example, when the elevated temperature is applied, the first surface of the first layer is a rotting fluid, or an additional layer, and - The first surface of the layer does not meet the matching requirements of the additional layer. The actual device of the present invention is designed to have a phase-lifting temperature such as a surface c or more. Therefore, the oxide of the second layer is preferably a refractory material. For example, glass 'melting and conveying materials' can operate at high temperatures up to t. The pt and PlRh test strips are suitable for clarifier panels. A suitable oxide for the second layer covering the outer surface of the clarifier panel Φ may be Ah〇3, Zr〇2, Mg0, Ti〇2'Si〇2, etc., as well as mixtures and combinations thereof. In a particular embodiment,

AhO+Zr〇2 is especially needed. In order to facilitate the application of the present day and month, Si is also included in the possible second metal group. In order to achieve a strong bond between the first layer and the second layer, and avoid between the first layer and the second layer after several cycles of operation, the first layer of metal and the second broad oxide are preferably substantially similar Thermal expansion coefficient (CTE). Under normal glass manufacturing conditions, pt, p, Rh, and A· have a CTE similar to 201026897. In a particular embodiment, we highly expect the second layer to be substantially dense, ie, no greater than 1 in the permeation. Voids and cracks. In a particular embodiment, we desire that the second layer is substantially free of voids and cracks greater than 5 〇〇 nm. In certain other embodiments, we desire that the second layer is substantially free of voids and cracks of A^300 nm. In a particular embodiment, we prefer that the second layer of germanium is substantially free of voids and cracks greater than 10 nm. The denser the second layer, the slower the thief rate of the fluid through the layer (such as 〇2 or other (4)), the more effective separation and protection of the first surface of the first $. In order to protect the first layer containing Pt from the atmospheric contact with && we hope that the second layer is substantially free of pt〇2 without voids and cracks. As explained previously, Pt and a undergo a bottom reaction 〇):

Pt (solid) + 〇2 (gas) <--> pt〇2 (gas) (1) ❹ The molecular size of Pt〇2 is significantly larger than 〇2, so there is a smaller space volume resistance of the dog through the second layer. . Therefore, if the voids and cracks of the second layer permit the rapid diffusion of 〇2, but the diffusion of Pt〇2 is prohibited, the reaction formula (丨) can quickly reach an equilibrium state, thereby avoiding further oxidation and pt loss. Thus, in a particular embodiment of the invention, it is highly desirable that the second layer be substantially compact, substantially inhibiting the diffusion of the first metal oxide in the gas phase under operating conditions. Therefore, under normal operating conditions of the device, when the first layer contains Pt B, we hope that the second layer (such as the Ah 〇 3 layer) is essentially not made 15 201026897 .

Pt〇2 from the voids and cracks that are diffused. In a particular embodiment, we prefer that the second layer be substantially free of voids and cracks to inhibit 〇2 diffusion under normal operating conditions. In a particular embodiment, we prefer that the second layer be substantially free of the second metal in the metallic state, i.e., the second metal of the second layer is completely oxidized. This fully oxidized second layer is very stable under normal operating conditions of the device. However, in certain embodiments, it may not be excluded that the second metal portion of the second layer is in a metallic state. It is also not excluded that a portion of the second metal in the metallic state forms a mixture of, for example, a metal under the second layer at the end of step (b). In those practical examples, we hope that if the design of the second layer is a violent path to the fluid, at least the surface of the second layer exposed to the fluid is completely oxidized. The second metal in the remaining metallic state, particularly the zone 相邻 adjacent to the first layer, can complement the second layer portion consumed during operation and is therefore desirable in certain embodiments. However, in other embodiments, since the second metal in the metallic state can be alloyed with the first metal, it may diffuse further into the first layer of the monolith during operation of the device, causing the first layer to weaken, and thus is not good. of. As described in the above summary, the interface between the first layer and the second layer of the device of the present invention is substantially superimposed. Therefore, when the interface is loaded with a plane substantially perpendicular to the plane of the center plane of the first layer to obtain a cross section, a roughness curve of Ι/zm resolution can be observed via an electron microscope. In a particular embodiment, the high laminated refractive index of the interface between the second layer and the second layer of the 16th 201026897 is an important feature distinguishing the present invention from the prior art coating metal. The laminated refractive index of the interface between the first layer and the second layer of the device of the present invention is 妓丨.48, at least ι% in the specific embodiment, at least 〇6〇 in the specific embodiment, and less in the specific embodiment. At least 1.80. • It can be explained that the thicker second layer provides the resistance of the fluid through its expansion. However, forming a thicker coating can be more costly and undesirable in certain embodiments. The second layer thickness is defined as the average shortest distance from the second profile-layer first surface that is further from the first layer. Thus, in a particular embodiment of the acoustics, the thickness of the second layer is at most 80 microns, and in other embodiments, up to 60 microns, and in some other embodiments, at most 5 microns, in certain other embodiments. Up to 40 microns in the middle, and up to 30 microns in certain other embodiments. In order to achieve a gated value that inhibits diffusion, the thickness of the layer of embodiment H is preferably at least 5 microns, in particular embodiments to: / 10 microns, in particular embodiments at least (9) microns in a particular embodiment. At least 30 microns. The stacking interface between the first layer and the second layer may include a specific interactive locking feature, that is, a specific portion of the first layer protrudes to the second layer, and/or a special portion of the second layer reaches the first layer . This interactive locking feature is particularly costly for a strong bond between the two layers. By conventional coating methods such as direct chemical vapor deposition of the second layer of oxide, it is less likely to form an interactive locking feature of the imicron solution. Because of the high interfacial adhesion strength and the low fluid (such as 〇2) diffusion rate, the interlocking feature with substantially no voids is still needed: it is difficult to form using conventional coating methods, but the present invention It can be achieved. In a particular implementation, the protruding portion of the first metal is preferably directly bonded to the first layer of the monolith, and/or the protruding portion of the second layer of oxide is directly bonded to the second layer of oxide of the monolith. This first layer and the first layer of continuous structure contribute to the bond strength between the first layer and the second layer. However, in certain embodiments, it is not excluded that the first metal-depleted particles of the second layer of the second metal oxide do not directly adhere to the first metal of the monolith. In the particular embodiment, it is not excluded that under the second layer, the first-thickness of the monolith is formed and the islands that capture the particular second metal oxide are not noticeable. * The high laminated refractive index of the interface between the first layer and the second layer provides a large interface between the two layers, @ this can improve the relationship between the two. The adhesion can be further improved if there is an interlocking feature. The protective coating of the second layer of the device of the present invention may reduce oxidation and loss of the first layer. In an embodiment, the first metal includes a heavy metal such as Pt, which protection can translate into significantly longer device life and cost savings. In other words, we know that due to the Pt〇2 dissociation in the cold zone and the condensation of metal Pt particles, the Pt oxidation in the glass manufacturing process may lead to the final Peptide in the glass of 201026897 and form an annoying defect. Therefore, the apparatus of the present invention can be suitably used in a glass manufacturing system, and the quality of the glass can also be improved. Figure 1 shows a broom electronic image showing a cross section of a metal A1 precursor Pt-Rh test piece. Figure 1 is a cross-sectional view of the structure and composition of the following. - ❹ @2 shows a scanning electron micrograph of a cross section of a 70-doped Ah3 layer Pt-Rh test piece prepared by the metallization process of the present invention described below. • Figure 3 shows the scanning electron micrograph of the surface of the pt_Rh substrate after removing the Ah〇3 layer on which it was originally formed. This image shows the stacked nature of the first surface of the *pt Rh layer. [I. Process of manufacturing the device: 第二 + The second item of the invention is a method for pouring the first layer-surface of the first metal to avoid oxidation at elevated temperatures when the air towel is oxidized, The method comprises the steps of: (4) providing a precursor layer comprising a second metal in a metallic state on at least a portion of the first surface of the first metal; the second metal may be alloyed with the first metal under the providing layer; And (6) exposing the precursor layer to oxidized air at elevated temperatures to form a second layer comprising the second metal oxide. Step (a) may include sputtering, chemical vapor deposition slurry deposition 201026897 to form a precursor layer of the first metal in the metallic state. The second metal may enter the first layer during step (a), and the first metal may enter the precursor layer, forming a first metal gradient and a second metal gradient in the interface at the same time. In a particular embodiment, the precursor layer preferably includes at least a top end portion that is substantially free of the first layer, and preferably the second metal does not penetrate the full thickness of the first layer. In certain other embodiments, the precursor layer comprises a mixture of the first metal and the second metal throughout the thickness. For example, if A1 is deposited on the surface of a Pt substrate, ® can form a precursor layer consisting essentially of P7 Aly. In the case where the first metal is Pt or Pt~Rh and the second metal is A1, the A1 layer can be deposited by sputtering, conventional chemical vapor deposition, slurry deposition, or the like. Since Pt and A1 are known to form an alloy represented by PtxAly, the interface thereof is thus a Pt-Al mixture of various Pt/Al molar ratios. The first metal, the first layer, and the second metal can be as described above along with the apparatus of the present invention. Therefore, the first metal may be a responsible metal such as a Pt or Pt-Rh test piece, and the second metal may be A1, Zr, Ti, Si, Mg, and a mixture and combination of these. The thickness of the precursor layer is defined as the average shortest distance from the surface of the precursor layer farther from the first layer to the first surface of the first layer. Here the concentration of the second metal is negligible. Thus, the thickness of the precursor layer is determined in part by the desired thickness of the last second layer of the second layer of oxide. In particular, when the first metal comprises pt and the second metal comprises A1, the thickness of the precursor layer preferably does not exceed 120 microns 20 201026897, in certain embodiments does not exceed 100 microns, and in particular embodiments does not exceed 80 microns. Not exceeding 60 microns in a particular embodiment, not in a particular embodiment

More than 50 microns, in certain embodiments no more than 4 microns. Nonetheless, in certain embodiments, a first layer requiring a precursor layer thickness of at least 2 Å to form an oxide of the second metal is relatively thick. Thus, in step (a), the thickness of the precursor layer in the particular embodiment is in the range of 20 microns to 6 microns, in certain other embodiments in the range of 20 microns to 50 microns, in certain other embodiments. The range is in the range of 25 microns to 45 microns, and in certain other embodiments is in the range of 30 microns to 40 microns. In step (a), various techniques can be used to form precursor layers such as conventional chemical vapor deposition, slurry deposition, _, New Zealand, and the like. While various techniques can achieve various thicknesses of the precursor layer, it should be understood that a particular treatment may be best suited to produce a metal coating of a particular thickness range. Therefore, if the metal layer at the beginning of the second layer is too thick to be completely oxidized to the second layer of the second layer, it is preferable to carry out the thinning step of the second metal precursor layer, for example, she: she is thankful (four) Ershun The scope of the need. What the temple does not need, the technology can form a gold-containing A1 directly, for example, in the deposition of the first 枓 containing Pt. This treatment produces a uniform thickness range of the A-Pt alloy layer of 2 Å and then a thin step. Micro-no, without need to be in a particular embodiment, step (4) may include a post-step 21 201026897 deposition heat treatment step prior to step (b). Prior to step (b), it is desirable to form a mixture comprising the first metal and the first metal to form a high overlap refractive index interface of the apparatus of the present invention. The deposition process of the specific thinning can be carried out at a temperature at a very low speed in the mixture or intermetallic metal between the first metal and the first metal. Prior to step (b), the post-deposition heat treatment step causes the interface to be heated above the deposition temperature to promote the formation of a metal mixture within the precursor layer. For example, we found that the conventional A1 CVD process can be performed at 50 (TC or less) to produce a Pt-tipped precursor A1 layer on an Al-Pt alloy substrate, and a post-deposition heat treatment at about 1000 〇c contributes to A1 and The formation of pt-mediated metal. Regardless of the technique used, we need to form an alloy between the first and second metals in step (a). Thus, the interface between the first layer and the precursor layer contains the first metal and The gradient of the two metals ranges from the region containing the negligible level of the second metal to the intermediate region exhibited by the alloy or mixture to the other end comprising the lowest level of the first metal. Thus, in a particular embodiment, the first metal Is Pt, the second metal is A1, and the interface ranges from a first layer mainly composed of the components of the pt group to an intermediate region represented by pt · Α 1 to a region mainly composed of Α 1. In another embodiment, the first metal Is the vapor, the second metal crucible 1, the interface ranges from the first layer surface mainly composed of the pt component to the intermediate portion represented by R • A1 to the other end mainly composed of the crucible seven. In the latter embodiment Precursor It may be particularly useful to include a mixture of Pt and A1 throughout the thickness due to the higher melting temperature of AhPt than A1. 22 201026897 In process step (b) of the present invention, the precursor layer is exposed to 02 at elevated temperatures. In the air, for example, the deuteration of the step (6) can be carried out in an air of 500 〇C or more, for example, 8 〇{rc or more, such as ◦C or more. In this case, the precursor layer is oxidized to the second layer. The first metal is composed of the present Pt ▲ the second metal is an example of the composition of the A1 as an example. The aluminum containing the surface region of the A1 precursor layer is first oxidized to Ah 〇 3. Then 〇 2 ^ diffuses through the AhCb layer, The underlying metal M is oxidized. At elevated temperatures, the second metal in the metallic state needs to be more reactive than the first metal containing (3), as is the case where the first metal is pt and the second metal is in the case of the A1 embodiment. In this case, 〇2 diffuses through the oxide layer formed on the first metal to reach the atom of the first metal in the intermediate region of the interface, and the first metal turns to the reduced metal due to the effect of the second metal reduction status. Therefore, it is preferable to oxidize the second metal in the step (6). Without wishing to be bound by a particular theory, we believe that the second metal oxide in the precursor layer will polymerize with the top oxide layer, while the first metal in the metal state will polymerize with the first layer of the monolith, eventually contiguous. A second layer having no voids is formed on the continuous first surface of the first layer. We also believe that the polymerization of the first metal and the second metal oxide in the precursor layer in step (b) occurs in a random manner, and at the end of step (b), a rough irregular shape of the first layer and the second layer is produced. surface. In a particular embodiment, the result will form an interactive locking feature of the //m scale. As described above and in the apparatus of the present invention, such a rough interface and cross-linking feature contributes to the strong adhesion of the second layer to the first layer. It can be understood that the thicker the precursor layer is, the thicker the Al2〇3 layer formed before the oxidation of all the metal A1 is. The more difficult it is at a given pressure and temperature of the 〇2 part, the longer it takes to diffuse the 〇2. The thick gram 2 〇 3 layer reaches the remaining A1 metal below. Therefore, the thickness range required for the precursor layer has been described above. In the case of the implementation of the economy, the second metal is required to be fully oxidized to a stable oxide under the oxidized gamma. This complete oxidation produces a stable layer of ruthenium which is no longer oxidized during normal operation of the forming apparatus. However, in a particular embodiment, it is not excluded that the second layer contains a non-negligible amount of metal in the second state in addition to the second metal oxide. In some applications, the strength of the first layer of structure is important, and the second metal entering and remaining in the first metal layer may unduly impair the strength of the first layer, so all of the second metal in the precursor layer is preferably To be oxidized in step (b). In some embodiments, the reduction in the strength of the bond due to alloying between the first metal and the remaining second metal is tolerable or negligible, and preferably allows a specific amount of the second metal to remain in the step ( b) finally alloying with the first metal and thus the remaining second metal may be further oxidized during operation of the device at a later stage. The repair or maintenance of the integrity of the second layer may also be compromised with processing conditions such as normal wear and tear. crack. As described above and in the apparatus of the present invention, we prefer that the interface between the first layer and the second layer in step (b) is substantially dense and has an irregular shape of 24 201026897. The first layer formed in the step (b) of the present invention, which is described in the apparatus of the present invention, may be such that the inter-layered refractive index between the first layer and the second layer is at least 1.50, in a particular embodiment. At least 丨55, in a particular embodiment at least 1. 6G' is at least h 65 in a particular embodiment, at least 1.7 在 in the embodiment, and at least 175 in the more embodiment. In a specific embodiment, at the end of step (b), the formed second layer comprising the second metal halide can effectively inhibit the diffusion of & metal. In certain other embodiments, at the end of step (6), the second layer formed may be 〇2 permeable, but still impermeable to the first metal orthorhombic oxide. For example, when the second metal is A1, the first metal is pt. Due to the significantly larger molecular size of pt〇2, the AhOs layer may play a more pronounced inhibitory layer than 〇2 to diffuse the aprons, effectively inhibiting the continuity of the metal Pt. Oxidation and removal. Therefore, a second metal oxide such as Ah3 can act as a protective layer to withstand oxidation of the first metal. In a particular embodiment of the process of the present invention, the elevated temperature in step (b) ranges from 100 (TC to the melting temperature of the first metal. We find that the second metal contained in the precursor layer is in the first When the layer is oxidized to a dense coating, a higher temperature is required to promote diffusion of 〇2 to the oxide layer, which is required for complete oxidation of the second metal. However, we hope that the oxidation step does not result in melting of the first layer. In certain other embodiments, the precursor layer is comprised of a first 25 201026897 metal-to-metal intermetallic mixture, and in step (b), the range of elevated temperatures: preferably from 1 ooor to the first The melting temperature of the mixture of the layers. This is because if the precursor layer is heated above its melting temperature, the material will melt and may flow out of the surface of the first layer, damaging the formation of a continuous and substantially dense second metal oxide. In a particular embodiment, in step (b), the precursor layer is preferably heated to a elevated temperature at a rate of temperature rise such that oxidation of the second metal does not occur as apparently molten metal exits the first metal. In the embodiment, the first metal is Pt and the second metal is A1, and we find that A1 is easy to form 4Pt at about 1 ° C by forming an alloy. (: Higher oxidation temperature is more desirable. 'Allows A1 to oxidize rapidly to gossip without substantially penetrating into the monolithic metal. However, the formation of a intermetallic is required to obtain a strong crucible.

Ah〇3 coating. We believe that the steeper rise in temperature in the oxidation step is advantageous for forming a dense, dense oxide layer. In a particular embodiment of the process of the invention, step (6) is carried out in a preheating step prior to the formation of the apparatus of the invention and the Qianqing system. For example, in one embodiment, the apparatus is a Pt sonic tube member manufactured by the present invention (10), and the Pt tube clarification tube is covered with a layer of Al-Pt alloy in the oxidation step of the elevated temperature. The manufacturing was completed before.埽裟1^ In other words, the hair of the hair can be operated in the temperature of 26 201026897 in the gas containing G, and the dress can be formed in the county. For example, in the embodiment, the device is a pt clarified tube manufactured by the treatment of the present invention and covered with Ah 〇 3 can be manufactured by the following steps: (1) depositing a layer containing A1 on the outer surface of the pt clarification tube; (2) mounting From the clarified tube produced in step (1) to the glass-fused system; and (3) the pre-heated glass-fused system causes the clarification member to oxidize the precursor layer containing A1 at a temperature at which the air towel is lifted to form a second layer. Ο III. Manufacture of glass processing: The third aspect of the present invention is a glass manufacturing process using the apparatus of the present invention. The glass manufacturing process includes (D melting the entire batch of material in the melting tank to obtain the glass melt; (2) processing the glass melt through the conduit to the downstream process; (3) adjusting: glass smelting; and (4) The glass spurs form the desired shape. One or more Φ devices of the present invention may be used in each of steps (1) through (4). For example, in step (1), the specific elements of the glass melting tank may be based on The present invention is a precious metal covered with an Ah〇3 and/or Zr〇2 layer; in the step (2), the 'transport system may have Alz〇3 and/or Zr〇2 covering the outer surface of the Pt-Rh pipe; In (3), the clarifier or the stirring chamber may be the apparatus of the present invention; and in the step (4), the apparatus including melt drawing, floating, slot drawing, or other forming treatment, such as smelting downward drawing The treated tube may be a Pt-containing device of the present invention, partially or entirely covered with A12〇3 and/or Zr〇2. Example:· 27 201026897 All Pt-Rh test pieces contain approximately 2% by weight ribs. Preparation - a series of clean Pt-Rh test pieces containing 20% by weight of Rh, followed by The treatment of the present invention utilizes a slurry deposition process or a CVD process to coat the metal with an A1-Pt. The Al-Pt coating produced on the Pt-Rh test piece is then observed and/or tested. 145{rc alumina covered

The Pt-Rh test piece is about 72 hours. Next, the resulting Ah〇3 coated Pt-Rh test piece was observed and/or tested. © Figure 1 shows a scanning electron micrograph of a cross section of a metal A1 precursor pt-R sample. The composition of the precursor layer, the first layer, and the interface can be determined by any suitable characterization method. For example, a scanning electron microscope (SEM) and an electronic microprobe (έρμα) can be used to determine the composition of a particular location within the precursor layer and/or the entire metal component. Please refer to Fig. 11〇3 is a layer of Ni plating to help prepare the cross section of the sample so it is not the Q part of the device; 111a and 111b are the main phases of the precursor layer, and the concentration of each component of each ingredient And a different physical structure, 113 is a whole block of Pt-Rh metal. The components determined by EPMA at various locations are listed in Table 1 below. 28 201026897 Table 1

The number of ugly components shown in Figure 1 Pt-Rh test piece

Lc is the length of the curved line segment connecting the two points on the interface. Fig. 2 is a cross-sectional broom electron micrograph of the Pt-Rh substrate including the fully oxidized secret layer 201, which is illustrated by the ribs described below. In this figure, 203 is a single piece of metal, and 2〇5 is a layer of stencil material to help prepare the cross section of the image processing.

Figure 3 is a broom electron micrograph of the surface of the pt_Rh substrate after removal of the Ah〇3 layer on which it was originally formed. This image shows the stacked nature of the first surface of the pt_Rh layer. Each coated test piece to be image-processed is protected by a resin to protect its cross section. Get a SEC photo of the prepared cross section. Approximately 20 such images were collected and analyzed for each test piece. In order to quantify the degree of deposition, the "deposited refractive index" is measured and calculated in the following manner. Backscattered images were collected at 20 kV on a JEOL 6610 SEM apparatus. 29 201026897 First collect low-magnification images (~10χ - 25x) so that the test strips can be seen from the whole. Approximately 10 images were collected from the upper and lower edges of the test piece. After selecting the position, focus and adjust the SEM image to ensure that the test strip is positioned horizontally in the field of view. Then 15 〇χ of backscattered electron images were collected at the maximum possible resolution. Use the NIH ImageJ program (http://rsbweb.nih.gov/ij/) to analyze the image. If necessary, the brightness and contrast can be adjusted to have a strong contrast between the disc area and the brightness of the Ah〇3 or Zr〇2 coating. No other (4) is performed on the image. The image is then digitized so that the pt Rh area shows pure black (the 昼 value 〇), while the rest of the image is pure white (the 昼 255 value). Then use the magic wand tool to circle the pt Rh area and measure its circumference. The length of the stacking interface is obtained after subtracting the horizontal and vertical lengths from the circumference. ❹ In order to maintain the quality and statistical significance of the data: (1) Collect the same number of enlarged L numbers ^ There are images: (10) With (1) the position of the touch surface: (m) From each sample 目 目The series (,; (5) with a high solution TIF^ set the heart image to clearly define the stack of the interface; (V) with the image that will not be lost _ free of image processing due to Shi Wei; 'during the analysis of the knife' Visually inspecting the image to ensure the correct edge, and not the winter (four) wave ^ Figure 4 shows the process of image processing to obtain the sample laminated refractive index. In the 30 201026897 _ domain 40 sample cross-section of the ® image, including pure area and eight compartments Gamma 1 purchase 4. 2, occupation (four) region and neat image _ 4 3, measurement (four) regional dirty week 2 = ^ delete, (10) length of hemp, then ten different as follows: Lc = Lp_L1_L2_L3. C! is again calculated as follows: CI = Lc / Ls = (Lp - U - L2 - L3) / L2.

In the four comparative examples, the pt_n maps obtained by direct deposition of ZrU coatings by electropolymerization were measured from different sources. According to this item, and the four comparative examples (CE1, corresponding image 5·2A) And 5 years old CE2, corresponding images 5. 3A and 5. 3B; CE3, corresponding images 5. 4A and 5 · 4B; and CE4, corresponding images 5. 5A and 5 · 5B) - sample samples (E1, corresponding Image 5.1A and 5.1.B) interface images. Larger images are placed in the left column (ie, images 5. u, 2A, 3A, 5. 4A, and 5·5A), while the enlarged image area surrounded by rectangles in the left block is placed in the right column (and image) 5.1Β, 5. 2Β, 5. 3Β, 5. 4Β and 5. 5β, respectively corresponding to 5·1Α, 5. 2Α, 5. 3Α, 5. 4Α and 5. 5Α).

The results of the image analysis are listed in Table II below. Table II sms' average number of stacked fold analysis (error is In) El 1-71 ±〇.〇8 21 CE1 1-46 ±〇.〇8 19 CE2 ~~ _ 1.43 ± 0.08 20 CE3 116±〇. 〇6 20 CE4 1·17±〇·〇5 20 31 201026897 The coated pt-Rh test piece has a more complicated interface than the test piece coated with zircon. It is apparent to those skilled in the art that the present invention is capable of various changes and modifications without departing from the spirit and scope of the invention. It is intended that the present invention cover the modifications and variations of the invention and the scope of the inventions BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in FIG. The same reference numbers represent the same or similar elements. Figure 1 shows a scanning electron microscope image of a pt containing the metal A1 precursor layer. Q Figure 2 shows a scanning electron microscope image of the Pt_Rh test piece carrying the fully oxidized Al2〇3 layer. • 胄3 is previously formed, then 3 layers are removed, pt, and the surface of the substrate is scanned. Cat electron microscope image. Figures 4 and 5 show image acquisition and analysis processes to obtain information processed on a pt_R substrate in accordance with a particular embodiment of the present invention. [Major component Fu Rui description] horizontal wear surface 100; Ming 1〇1; key layer 103; precursor layer various main phases 32 201026897 * 105,107,109, llla,lllb,111; monolithic Pt-Rh metal 113; fully oxidized Al2 〇 3 layers 201; monolithic metal 203; tantalum material 205; oxidized region 401. ❿ ❿ 33

Claims (1)

201026897 VII. Patent Application 1. A device comprising: (i) having a first layer comprising a first surface of a first metal; and (ii) a second layer comprising a second metal oxide, directly bonded a first first surface and covering at least a portion of at least the first surface of the first layer (A) the interface between the first layer and the second layer is substantially dense and irregular in shape; and (B) When the second metal is deposited on the first surface of the first metal at an elevated temperature, the second metal may be alloyed with the first metal. 2. According to the application for the scope of patents»1, wherein (C) consists of a metal film composed of a second metal and a first metal mixture, the thickness is substantially equal to the second layer of the inert substrate branch, when the film The main surface is exposed to air in a temperature range from a circle. (: to the melting temperature of the first metal - the segment is sufficient when the gate is _ can be completed, the silk is solid on the wire ^ 3. According to the scope of claim 1 or 2, the precious metal And the second metal comprises at least one A1, wherein: the first metal comprises Zr and Si. 4. According to the scope of claim 1 or 2, the second layer consists essentially of Al2〇3. : The first layer comprises a device of Pt 5 · Depending on the patent group or 2 items, wherein the second layer is impermeable to the oxide of the first metal. 6. According to the patent application range 1 or 2 The device is impervious. The second layer is substantially 34. 201026897 7. According to the scope of the patent or the device of the second item, the interface between the first layers has a laminated refractive index of at least 1 50., =:= Item 1 or 2, wherein the second layer has a thickness ===(four) or 2 kisses, and the material is fused to the glass ginseng 10. According to the device of claim 1 or 2, the clarifier tube of the system is melted. Set to glass soluble φ :===: r device' wherein the device is set to a stirring tank 12. According to the device of claim 1 or 2, the covering is covered. 13. A device according to claim 1 or 2 wherein the skirt is a flange. 14. Apparatus according to claim 1 or 2 wherein the second layer covers substantially all exposed surfaces of the device and the side is exposed to an atmosphere containing oxygen. 15. A device according to the scope of claim 2 or 2 wherein the device surface is covered by a second layer. ° 16. A method of preventing oxidation of a first layer of a first surface of a first metal comprising a first metal when exposed to oxidizing air at elevated temperatures. The method comprises the steps of: (a) first in the first metal a second metal fresh precursor layer is provided on at least a portion of the surface, the second metal may be alloyed with the first metal in the case of formation; and (b) by exposing the precursor layer to elevated temperatures In the oxidizing atmosphere, shape 35 201026897 into a second layer containing a second metal oxide. 17. The method of claim 16, wherein the first layer comprises pt. 18. The method of claim 16 or 17, wherein the first layer comprises Pt and the second metal comprises at least one of Al, Si and Zr. 19. The method of claim 16 or 17, wherein the precursor layer has a thickness of from 7 micrometers to 120 micrometers in step (a). 20. The method of claim 16 or 17, wherein at the end of steps (b) & the interface between the first and second layers is substantially dense and has an irregular shape. The method according to claim 16 or 17, wherein the second layer is formed in the step (b) such that the interface between the first layer and the second layer has a laminated refractive index of at least 1.5 Å. 22. The method according to claim 16 or 17, wherein the silk layer provided in step (a) comprises substantially a mixture of the first and second metals. 23. The method according to claim 16 or 17, wherein in step 卬) ’, the temperature is raised from 1000 ° C to the first metal melting temperature. 24. According to the method of claim 16 or 17, wherein in step (b), the elevated temperature is 1000. It is within the range of the melting temperature of the precursor layer. The method according to claim 16 or 17, wherein at the end of the step (6), the second metal is completely converted into its oxide in the precursor layer. The method according to claim 16 or 17, wherein in the step (8), the precursor layer is heated to a lifting temperature, and the temperature is raised to cause the second metal to oxidize without significantly melting the second metal. Spider 16 or 17 of which is a step package 36 201026897 One less chemical vapor deposition, coated powder bath method, charge coating, spray = according to ^ _ 6 or 17 Huanzhi preheating step. y The method of item 16 417, wherein step (8) is performed in situ when the device is installed in the system. 30. According to the scope of application for patents 29 溶 melting and / or transfer system. The method of shooting the operating system is glass 31. According to the patent application range, the St layer has a thickness of two = the range of 1 or =1, and the method of applying the special clarifier item, wherein the device is used For the pitch, 37