Patent Application
20140069988
The present disclosure generally relates to methods of using active braze techniques in high temperature rechargeable batteries. In some specific embodiments, the present disclosure relates to a method of sealing a portion of an insulated collar and a metal ring of a sodium metal halide battery.
High-temperature rechargeable batteries, such as sodium metal halide or sodium sulfur cells, have a number of components that need to be sealed for the cell to work. Sodium metal halide batteries, for instance, include a sodium metal anode and a metal halide (NiCl2 for example) cathode. Beta″-alumina solid electrolyte (BASE) separator is used to separate the anode and cathode. The solid electrolyte allows the transport of sodium ions between anode and cathode. A secondary electrolyte (NaAlCl4) is also used in the cathode mixture. The cathode mixture consists of nickel and sodium chloride along with other additives. The cathode mixture is contained inside the BASE tube, which is closed on one end.
The present design of Na—NiCl2 battery cell entails having the open end of this beta-alumina ceramic tube joined to an alpha-alumina collar using a glass seal. Spinel may also be used as a collar material in Na—NiCl2 batteries. The collar is in turn joined with nickel rings with the help of thermal compression bonding (TCB). TCB is achieved through metallizing the alpha-alumina or spinel collar. The design of the present cell demands this seal to be resistant towards molten sodium and molten halide (sodium melts at 98° C. and NaAlCl4 melts at 157° C.). The glass seal and TCB are two of the weak links in the present design for a path to long life: the glass seal and TCB encounter corrosion from sodium and halide and, because of this, are found to degrade over time.
There are two ways to address this problem; one is by improving the glass seal and TCB in terms of degradation from sodium and halide corrosion; and the second is by completely getting rid of the glass seal and the TCB in the design of the cell. The use of this glass seal can be eliminated by using a graded ceramic (beta-alumina tube with alpha-alumina header) tube. However, in the design where this graded tube is used, the nickel ring cannot be joined with the alpha-alumina collar using a TCB-like process. Therefore, alternate joining technologies are necessary.
Active brazing is a procedure in which one of the components from a braze alloy reacts with ceramic and forms an interfacial bond. The requirement of a braze alloy for use in high temperature rechargeable batteries is high corrosion resistance towards sodium and halide. Conventionally, brazing is done through metallization in combination with a braze alloy. However, metallization (for example with Mo) is typically carried out at a temperature of about 1550° C., a temperature too high for beta-alumina, because of the loss of soda (Na2O). Therefore, metallization is not an appropriate procedure for the beta-alumina tube found in these cells. Further, the metallization/TCB process is complicated and expensive. Active brazing has been known in the literature to join ceramic to metal, but there are not many active braze alloys (ABAs), particularly high temperature (900-1250° C.) ABAs which are resistant to corrosion from sodium and halide available commercially.
There continues to be a growing need in the art for high performance metal halide batteries with lower fabrication costs. Prior attempts for achieving this have utilized reticulated carbon foams and meshes. However, these materials frequently do not allow for even distribution across the cathode. Additionally, they are often more expensive than the nickel they are trying to replace. The methods of introducing these materials to the cathode can be quite arduous and difficult to put into commercial large scale operation. Thus, it may be desirable to have an electrode material that maintains the performance of the battery, but allows for a reduction in costs over those materials currently available.
The present disclosure provides, in a first aspect, a method of joining spinel with metal or a metal alloy by active brazing. This method includes introducing a braze alloy composition between the metal or metal alloy and the spinel to be joined and heating the components to form an active braze seal (joint) between the spinel and the metal or metal alloy. In this embodiment, the braze alloy composition comprises nickel and an active metal element, and further comprises a) germanium, b) niobium and chromium or c) silicon and boron. Alternatively, the braze alloy composition comprises copper, nickel and an active metal element. The components are then heated to form an active braze seal (joint) between the spinel and the metal or metal alloy.
The present disclosure provides, in a second aspect, a method of joining metal or a metal alloy and alpha-alumina by active brazing. This method includes introducing a braze alloy composition between metal or a metal alloy and the alpha-alumina to be joined and heating the components to form an active braze seal (joint) between the metal or a metal alloy and the alpha-alumina. In this embodiment, the braze alloy composition comprises nickel and an active metal element, and further comprises a) germanium, b) niobium and chromium or c) silicon and boron. Alternatively, the braze alloy composition comprises copper, nickel and an active metal element. The components are then heated to form an active braze seal (joint) between the alpha-alumina and the metal or metal alloy.
The present disclosure provides, in a third aspect, a method for providing a seal between a first component and a second component of a sodium-based thermal battery. This method includes introducing a braze alloy composition between metal or metal alloy and the spinel or alpha-alumina to be joined; and heating the components to form an active braze seal (joint) between the spinel or alpha-alumina and the metal or metal alloy. In this embodiment, the braze alloy composition comprises nickel and an active metal element, and further comprises a) germanium, b) niobium and chromium or c) silicon and boron. Alternatively, the braze alloy composition comprises copper, nickel and an active metal element. The components are then heated to form an active braze seal (joint) between the alpha-alumina and the metal or metal alloy.
These and other objects, features and advantages of this disclosure will become apparent from the following detailed description of the various aspects of the disclosure taken in conjunction with the accompanying drawings.
Each embodiment presented below facilitates the explanation of certain aspects of the disclosure, and should not be interpreted as limiting the scope of the disclosure. Moreover, approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about,” is not limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
In the following specification and claims, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. As used herein, the terms “may” and “may be” indicate a possibility of an occurrence within a set of circumstances; a possession of a specified property, characteristic or function; and/or qualify another verb by expressing one or more of an ability, capability, or possibility associated with the qualified verb. Accordingly, usage of “may” and “may be” indicates that a modified term is apparently appropriate, capable, or suitable for an indicated capacity, function, or usage, while taking into account that in some circumstances, the modified term may sometimes not be appropriate, capable, or suitable.
The disclosure includes embodiments related to methods of sealing portions of an electrochemical cell, for example a metal halide battery such as a sodium/sulfur or a sodium metal halide battery, by utilizing a braze alloy composition. As discussed in detail below, some of the embodiments of the present invention provide a method for sealing a spinel component to a metal or metal alloy component for a metal halide battery. Other embodiments relate to methods of joining alpha-alumina to metal or metal alloy by utilizing a braze alloy composition. By decreasing the need for metallization and TCE, these embodiments allow for fewer steps to be undertaken, decreasing the cost of the fabrication of the battery. Though the present discussion provides examples in the context of a metal halide battery, these processes can be applied to many other applications which utilize ceramic-to-metal and/or spinel-to-metal joining.
The use of active brazing in embodiments of this disclosure has a number of benefits. First, active brazing eliminates the weak links such as TCB in the battery. Second, it potentially reduces the number of steps necessary and the high temperature processing involved with metallization. Third, active brazing has the promise of long life and, thus, high reliability. Finally, active brazing is very cost effective. In short, active brazing decreases the number of process steps and increases reliability and performance of the cell. While some uses of active brazing are known in the literature, there are not many high temperature active braze alloys available commercially. Alloys suitable for use in high temperature rechargeable batteries need to be compatible with the battery chemistry and should be able to be brazed below 1250° C. and above 1000° C.
Typically, “brazing” uses a braze material (usually an alloy) having a lower liquidus temperature than the melting points of the components (i.e. their materials) to be joined. The braze material is brought to or slightly above its melting (or liquidus) temperature while protected by a suitable atmosphere. The braze material then flows over the components (known as wetting), and is then cooled to join the components together. As used herein, “braze alloy composition” or “braze alloy”, “braze material” or “brazing alloy”, refers to a composition that has the ability to wet the components to be joined, and to seal them. A braze alloy for a particular application should withstand the service conditions required, and melt at a lower temperature than the base materials or melt at a very specific temperature. Conventional braze alloys usually do not wet ceramic surfaces sufficiently to form a strong bond at the interface of a joint. In addition, the alloys may be prone to sodium and halide corrosion.
As used herein, the term “brazing temperature” refers to a temperature to which a brazing structure is heated to enable a braze alloy to wet the components to be joined, and to form a braze joint or seal. The brazing temperature is often higher than or equal to the liquidus temperature of the braze alloy. In addition, the brazing temperature should be lower than the temperature at which the components to be joined may not remain chemically, compositionally, and mechanically stable. There may be several other factors that influence the brazing temperature selection, as those skilled in the art understand.
Embodiments of the present invention provide a braze alloy composition capable of forming a joint by “active brazing” (described below). In some specific embodiments, the composition also has high resistance to sodium and halide corrosion. In some embodiments, the braze alloy composition includes nickel and an active metal element, and further comprises a) germanium, b) niobium and chromium or c) silicon and boron. Alternatively, the braze alloy composition comprises copper, nickel and an active metal element, as described herein. Each of the elements of the alloy contributes to at least one property of the overall braze composition, such as liquidus temperature, coefficient of thermal expansion, flowability or wettability of the braze alloy with a ceramic, and corrosion resistance. Some of the properties are described below.
“Active brazing” is a brazing approach often used to join a ceramic to a metal or a metal alloy. It may also be used to join spinel with metal or a metal alloy. Active brazing uses an active metal element that promotes wetting of a ceramic or spinel surface, enhancing the capability of providing a hermetic seal. An “active metal element”, as used herein, refers to a reactive metal that has higher affinity to the oxygen compared to the affinity of element in ceramic and thereby reacts with the ceramic. A braze alloy composition containing an active metal element can also be referred to as an “active braze alloy.” The active metal element undergoes a decomposition reaction with the ceramic, when the braze alloy is in molten state, and leads to the formation of a thin reaction layer on the interface of the ceramic and the braze alloy. The thin reaction layer allows the braze alloy to wet the ceramic surface, resulting in the formation of a ceramic-metal or a spinel-metal joint/bond, which may also be referred to as “active braze seal.”
Thus, an active metal element is an essential constituent of a braze alloy for employing active brazing. A variety of suitable active metal elements may be used to form the active braze alloy. The selection of a suitable active metal element mainly depends on the chemical reaction with the ceramic (e.g., alpha alumina or spinel) to form a uniform and continuous reaction layer, and the capability of the active metal element of forming an alloy with a base alloy (e.g. Ni—Ge alloy). An ‘active’ element will react with the ceramic, forming a reaction layer between the ceramic and the molten braze that will reduce the interfacial energy to such a level that wetting of the ceramic takes place. The active metal element for embodiments herein is often titanium. Other suitable examples of the active metal element include, but are not limited to, zirconium, hafnium, and vanadium. A combination of two or more active metal elements may also be used. In some specific embodiments, the braze alloy includes titanium.
The presence and the amount of the active metal may influence the thickness and the quality of the thin reactive layer, which contributes to the wettability or flowability of the braze alloy, and therefore, the bond strength of the resulting joint. The active metal element is generally present in small amounts suitable for improving the wetting of the ceramic surface, and forming the thin reaction layer, for example, less than about 10 microns. A high amount of the active metal layer may cause or accelerate halide corrosion.
For the purpose of this disclosure, a “base metal” refers to the metal which has the highest weight percent in the alloy. In some embodiments, the base metal is nickel. In other embodiments, the base metal is copper.
The braze alloy composition may further include at least one alloying element. The alloying element may provide further adjustments in several required properties of the braze alloy, for example coefficient of thermal expansion, liquidus temperature and brazing temperature. In one embodiment, the alloying element can include, but is not limited to, cobalt, iron, chromium, niobium or a combination thereof.
As used herein, the term “liquidus temperature” generally refers to a temperature at which an alloy is transformed from a solid into a molten or viscous state. The liquidus temperature specifies the maximum temperature at which crystals can co-exist with the melt in thermodynamic equilibrium. Above the liquidus temperature, the alloy is homogeneous, and below the liquidus temperature, more and more crystals begin to form in the melt with time, depending on the alloy. Generally, an alloy, at its liquidus temperature, melts and forms a seal between two components to be joined.
The liquidus temperature can be contrasted with a “solidus temperature”. The solidus temperature quantifies the point at which a material completely solidifies (crystallizes). The liquidus and solidus temperatures do not necessarily align or overlap. If a gap exists between the liquidus and solidus temperatures, then within that gap, the material consists of solid and liquid phases simultaneously (like a “slurry”).
“Sealing” is a function performed by a structure that joins other structures together, to reduce or prevent leakage through the joint between the other structures. The seal structure may also be referred to as a “seal.”
An electrically insulating collar 60, which may be made of alpha-alumina or spinel, is situated at a top end 70 of the tube 20. A cathode current collector assembly 80 is disposed in the cathode chamber 50, with a cap structure 90, in the top region of the cell. The collar 60 is fitted onto the top end 70 of the separator tube 20, and is sealed by a glass seal 100 in an existing battery design. In one embodiment, the collar 60 includes an upper portion 62, and a lower inner portion 64 that abuts against an inner wall of the tube 20, as illustrated in
In order to seal the cell 10 at the top end (i.e., its upper region), and to ensure anode and cathode are chemically and physically separate from each other, and from the collar 60 in the corrosive environment, a ring 110 made of metal or a metal alloy is disposed, covering the collar 60, and joining the collar with the current collector assembly 80, at the cap structure 90. The ring 110 has two portions; an outer ring 120 and an inner ring 130, which are joined, respectively, with the upper portion 62 and the lower portion 64 of the collar 60, by means of the active braze seal 140. The active braze seal 140 is provided by the braze alloy composition described above. The collar 60 and the ring 110 may be temporarily held together with an assembly (e.g., a clamp) or by other techniques, if necessary, until sealing is complete.
The outer ring 120 and the inner ring 130 are usually welded shut to seal the cell, after joining with the collar 60 is completed. The outer ring 120 can be welded to the cell case 30; and the inner ring 130 can be welded to the current collector assembly 80.
The shapes and size of the several components discussed above with reference to
Embodiments of the disclosure provide a method for joining two components by using a braze alloy composition. The method includes the steps of introducing the braze alloy between the two components to form a brazing structure. The alloy may be introduced on either or both of the mating surfaces. The brazing structure can then be heated to form an active braze seal between the two components. In one embodiment, the first component includes spinel and the second component includes a metal or a metal alloy. In another embodiment, the first component includes alpha-alumina and the second component includes a metal or a metal alloy.
As discussed above, a braze alloy composition may provide an active braze seal to join components in the cell. One embodiment relates to active brazing on spinel. Spinel can be joined with a metal (such as nickel) using an active braze alloy composition. The assembly is heated to a temperature above (approximately 35° C. higher) liquidus of the alloy. A reaction layer with a metallic to semi-metallic nature forms at the surface of the spinel and is responsible for the wetting of spinel by the braze alloy.
One embodiment of the disclosure relates to a method of joining a metal or a metal alloy component to a spinel component with a braze alloy composition. Referring to
One embodiment of the disclosure relates to a method of joining a metal or a metal alloy component to an alpha-alumina component with a braze alloy composition. Referring to
The braze alloy composition for use in this disclosure must exhibit good strength and ductility as well as good phase stability at high temperatures. The braze alloy composition is comprised of a base metal and a melting point depressant which reduces the melting point of the overall composition. As used herein, the term “melting point depressant” refers to an element which may depress the melting point of the resulting alloy, when added to another element or an alloy. The melting point depressant element may decrease the viscosity and, in turn, increase the flowability (also referred to as wettability) of the braze alloy, at an elevated temperature. It may also influence the liquidus temperature and phase stability of the alloy.
According to some embodiments of the disclosure, the base metal for the braze alloy is nickel, which is relatively inert in corrosive environments as compared to other known base metals, such as chromium. In some embodiments, the braze alloy composition is based on a nickel-germanium (Ni—Ge) binary alloy. In some embodiments, the braze alloy composition includes nickel, an active metal element and germanium. Germanium is a melting point depressant. In some embodiments, the braze alloy includes germanium in an amount greater than about 5 weight percent, and the active metal element in an amount less than about 10 weight percent. In order to reduce the liquidus temperature, at least one additional melting point depressant, such as silicon, palladium, copper, and/or manganese, or a combination thereof, may further be added. These additional melting point depressants may further decrease the viscosity (increase the wettability) of the braze alloy. Generally, Ni—Ge binary alloys exhibit good strength, ductility, and good phase stability at high temperatures. The presence of germanium in the braze alloy may influence the liquidus temperature, and phase stability of the alloy. As a eutectic composition, the Ni—Ge binary alloy tends to be brittle. In one embodiment, hypo-eutectic compositions of the Ni—Ge binary alloy may be desirable. Hypo-eutectic compositions of Ni—Ge binary alloys are compositions containing an amount of germanium less than the amount of germanium in the eutectic composition. Controlling the amount of germanium in the braze alloy provides control over the liquidus temperature, thermal expansion coefficient, and phase stability of the alloy. In some embodiments of this invention, a suitable range for the amount of germanium is less than about 50 weight percent, based on the total weight of the braze alloy. In some embodiments, germanium is present from about 10 weight percent to about 50 weight percent, based on the total weight of the braze alloy. In some specific embodiments, germanium is present from about 20 weight percent to about 40 weight percent, based on the total weight of the braze alloy.
The hypo-eutectic compositions of the Ni—Ge alloys usually have a high liquidus temperature based on their composition. In order to reduce the liquidus temperature, additional melting point depressants may be added. Suitable examples of the additional melting point depressant include, but are not limited to, silicon, palladium, boron, copper, manganese, or a combination thereof. These additional melting point depressants may further decrease the viscosity (increase the wettability) of the braze alloy.
A suitable amount of the additional melting point depressant may be less than about 20 weight percent, based on the total weight of the braze alloy (but excluding the amount of germanium). In some embodiments, the braze alloy includes up to about 15 weight percent of the additional depressants. A suitable range is often from about 1 weight percent to about 10 weight percent. In some specific embodiments, the braze alloy includes up to about 10 weight percent palladium, based on the total weight of the braze alloy. In some embodiments, the braze alloy includes up to about 10 weight percent silicon, based on the total weight of the braze alloy. In some embodiments, the braze alloy includes up to about 5 weight percent boron, based on the total weight of the braze alloy. In some embodiments, a small amount of each of silicon or boron (e.g., less than about 5 weight percent) is used, as each of these may react with the active metal element (e.g. titanium) to form high-melting alloys. (All of these ranges are calculated with the exclusion of the germanium level).
In some embodiments, the braze alloy composition includes nickel, an active metal element, and silicon and boron. Addition of an active metal element, especially titanium, could be technically very challenging due to the possibility of titanium boride formation, in that the formation of titanium boride may not allow any titanium to be used as the active element. However, it was observed that titanium in these alloys is not captured in titanium boride form.
In some embodiments, the braze alloy composition includes nickel, an active metal element, and niobium and chromium. In some embodiments, niobium is present in an amount from about 14 weight percent to about 20 weight percent. In some embodiments, chromium is present in an amount from 2 weight percent to about 28 weight percent. In some embodiments, an alloying element may further be present in the braze alloy to adjust several properties of the braze alloy, such as corrosion resistance, liquidus temperature, brazing temperature, and mechanical properties of the alloy. Examples of suitable alloying elements include cobalt, molybdenum, tungsten, niobium, and tantalum. In some embodiments, the first braze alloy may include up to about 10 weight percent cobalt. Addition of a melting point depressant may reduce the melting point of the overall composition. A suitable range for the amount of palladium is from about 0 weight percent to about 10 weight percent to lower the melting point. One example of the nickel, active metal, niobium/chromium braze alloy composition is Ni-28Cr-14Nb-9Co-5Ti.
In some embodiments, the braze alloy composition further includes iron, chromium, or a combination thereof. In some embodiments, iron is present in an amount less than about 10 weight percent, based on the total weight of the braze alloy. In some embodiments, chromium is present in an amount less than about 10 weight percent, based on the total weight of the braze alloy. Silicon and boron are melting point depressants. Addition of a melting point depressant may reduce the melting point of the overall composition. A suitable range for the amount of silicon is from about 2 weight percent to about 10 weight percent. In some embodiments, a small amount of each of silicon or boron (e.g., less than about 5 weight percent) is desirable, as each of these may react with the active metal element (e.g. titanium) to form high-melting alloys. In some embodiments, an alloying element may further be present in the braze alloy to adjust several properties of the braze alloy, such as corrosion resistance, liquidus temperature, brazing temperature, and mechanical properties of the alloy. Examples of suitable alloying elements include cobalt, molybdenum, tungsten, niobium, and tantalum. In some embodiments, the first braze alloy may include up to about 50 weight percent cobalt. Each of the other alloying elements may be present in an amount up to about 5 weight percent, based on the total weight of the braze alloy. One example of the nickel, active metal, silicon/boron braze alloy composition is Ni-7Cr-4.5Fe-4.5Si-3.2B-2Ti.
According to some embodiments of the disclosure, the base metal for the braze alloy is copper. In some embodiments, the braze alloy composition includes copper, an active metal element, and nickel. Development of this braze alloy is driven from abundant and inexpensive copper in the formulation. In addition, copper is a highly ductile metal, and thus copper based alloys (with high content of copper) can be processed using a wide variety of cost-effective techniques such as rolling, melt spinning and powder atomization. Nickel can function as a chemically-inert element in a corrosive environment, and thus improves the corrosion resistance of the alloy composition. The addition of nickel may also increase the melting temperature of the alloy composition. In some of these embodiments, nickel may be present in an amount less than about 30 weight percent, based on the total weight of this braze alloy. A suitable amount of nickel may range from about 3 weight percent to about 25 weight percent.
This braze alloy composition may further include at least one alloying element. The alloying element may provide further adjustments in several required properties of the braze alloy, for example coefficient of thermal expansion, liquidus temperature, brazing temperature, corrosion resistance, and strength of the braze alloy. In one embodiment, the alloying element can include, but is not limited to chromium, niobium, cobalt, iron, molybdenum, tungsten, palladium, or a combination thereof. In some embodiments, the braze alloy includes up to about 4 weight percent chromium, based on the total weight of the braze alloy. In some embodiments, the braze alloy includes up to about 1 weight percent molybdenum, based on the total weight of the braze alloy. In some embodiments, the braze alloy includes up to about 2 weight percent niobium, based on the total weight of the braze alloy. In some embodiments, the braze alloy may further include palladium. Addition of palladium may improve corrosion resistance of the overall composition. The braze alloy may include up to about 40 weight percent palladium, based on the total weight of the braze alloy. The braze alloy composition provides high resistance to sodium corrosion resistance, and can provide moderate corrosion resistance in a halide-containing environment. Three examples of this copper, active metal, nickel braze alloy are shown below:
(i) Cu-3Ni-1Ti
(ii) Cu-10Ni-2Ti
(iii) Cu-10Pd-15Ni-2Cr-0.5Mo-2Ti.
The presence and the amount of the active metal may influence the thickness and the quality of the thin reactive layer, which contributes to the wettability or flowability of the braze alloy, and therefore, the bond strength of the resulting joint. In some embodiments, the active metal is present in an amount less than about 10 weight percent, based on the total weight of the braze alloy. A suitable range is often from about 0.5 weight percent to about 5 weight percent. In some specific embodiments, the active metal is present in an amount ranging from about 1 weight percent to about 3 weight percent, based on the total weight of the braze alloy. The active metal element is generally present in small amounts suitable for improving the wetting of the ceramic surface, and forming the thin reaction layer, for example, less than about 10 microns. A high amount of the active metal layer may cause or accelerate halide corrosion.
The braze alloy composition may further include at least one alloying element. The alloying element may provide further adjustments in several required properties of the braze alloy, for example coefficient of thermal expansion, liquidus temperature and brazing temperature. In one embodiment, the alloying element can include, but is not limited to, cobalt, iron, chromium, niobium or a combination thereof. In some embodiments, the braze alloy includes up to about 30 weight percent (e.g., about 1%-30%) of the alloying element, based on the total weight of the braze alloy. In some specific embodiments, the braze alloy includes up to about 10 weight percent chromium, based on the total weight of the braze alloy. In other specific embodiments, the braze alloy includes up to about 10 weight percent niobium, based on the total weight of the braze alloy. In some embodiments, the braze alloy includes up to about 20 weight percent of iron, based on the total weight of the braze alloy. In some specific embodiments, the braze alloy includes up to about 30 weight percent of cobalt, based on the total weight of the braze alloy.
The braze alloy composition consists of an element (for example, titanium), which has higher free energy of formation for oxides compared to aluminum. In some embodiments, this braze alloy composition is used as a foil (or paste) between metal or a metal alloy and alpha-alumina or spinel. This assembly is heated in dry argon to a temperature higher than the liquidus temperature of the alloy. Without being held to any one theory, it is believed that the active element (for example, Ti) reacts with the spinel or alpha-alumina to form titanium suboxides on the interface, which results in cohesive bonding between two components.
This is demonstrated in
In some embodiments, a layer of the braze alloy is disposed on at least one surface of either or both of the components to be joined by brazing. The thickness of the alloy layer may be in a range between about 5 microns to about 100 microns. In some specific embodiments, the thickness of the layer ranges from about 10 microns to about 50 microns. The layer may be deposited or applied on one or both the surfaces to be joined, by any suitable technique, e.g. by a printing process or other dispensing processes. In some instances, the foil, wire, or the preform may be suitably positioned for bonding the surfaces to be joined.
The method further includes step of heating the brazing structure at the brazing temperature. When the brazing structure is heated at the brazing temperature, the braze alloy melts and flows over the surfaces. To achieve good flow and wetting of the braze alloy, the brazing structure is held at the brazing temperature for a few minutes after melting of the braze alloy, and this period may be referred to as “brazing time”.
The brazing temperature and the brazing time may influence the quality of the active braze seal. The brazing temperature is generally less than the melting temperatures of the components to be joined, and higher than the liquidus temperature of the braze alloy. In one embodiment, the brazing temperature ranges from about 900 degrees Celsius to about 1500 degrees Celsius for about 1 minute to about 30 minutes. In a specific embodiment, the heating is carried out a the brazing temperature from about 1000 degrees Celsius to about 1300 degrees Celsius for about 5 minutes to about 15 minutes. In one embodiment, the brazing temperature is held constant in a range of about 1050 to about 1100 degrees Celsius for about 15 minutes, then is held constant at a temperature in a range of about 1150 to about 1250 degrees Celsius for about 15 minutes. The expression “from about X degrees Celsius to about Y degrees Celsius” means that the process is carried out either by maintaining any temperature between X° C. and Y° C. or by varying the temperature within that range. To be perfectly clear, the expression “from about 900 degrees Celsius to about 1500 degrees Celsius” means that the process is carried out either by maintaining any temperature between 900° C. and 1500° C. or by varying the temperature within that range.
As discussed above, the braze alloy has a liquidus temperature lower than the melting temperatures of the components to be joined. In one embodiment, the braze alloy has a liquidus temperature of at least about 850 degrees Celsius. In one embodiment, the braze alloy has a liquidus temperature from about 850 degrees Celsius to about 1300 degrees Celsius, and in some specific embodiments, from about 950 degrees Celsius to about 1250 degrees Celsius.
The active braze alloy composition used will contribute to the parameters for heating. Clearly the parameters must be such that the components themselves are not damaged, but the heating will have to be such that liquidus is achieved. In most embodiments, the heating comprises holding the brazing temperature constant for about 1 minute to about 30 minutes after the braze alloy composition becomes substantially liquid. The heating temperature used, as well as the total heating time and the temperature ramp-up characteristics, depends on the braze alloy composition being used.
As described above, one example of a braze alloy that may be used in embodiments herein is an alloy of nickel-germanium-active metal. One representative heating profile for this alloy is shown in
The heating may be carried out in a number of different atmospheres. The heating can be undertaken in a controlled atmosphere, such as argon, hydrogen, nitrogen, helium; or in a vacuum. In most embodiments of the invention, the heating is performed in an ultra high pure argon atmosphere (that is, 99.99998%), dry helium, an atmosphere of 1%-5% hydrogen (balanced by argon), or a vacuum.
During brazing, the active metal element (or elements) present in the melt decomposes, and forms a thin reactive layer at the interface of the ceramic surface and the braze alloy, as described previously. The thickness of the reactive layer may range from about 0.1 micron to about 2 microns, depending on the amount of the active metal element available to react with the component, the surface properties of the component, brazing temperature and brazing time. The brazing structure is then subsequently cooled to room temperature; with a resulting, active braze seal between the two components. In some instances, rapid cooling of the brazing structure is permitted.
The examples presented herein are intended to be merely illustrative, and should not be construed to be any sort of limitation on the scope of the claimed invention. Unless specified otherwise, all of the components are commercially available from common chemical suppliers.
While several aspects of the present disclosure have been described and depicted herein, alternative aspects may be effected by those skilled in the art to accomplish the same objectives. Accordingly, it is intended by the appended claims to cover all such alternative aspects as fall within the true spirit and scope of the disclosure.
The present invention has been described in terms of some specific embodiments. They are intended for illustration only, and should not be construed as being limiting in any way. Thus, it should be understood that modifications can be made thereto, which are within the scope of the invention and the appended claims. Furthermore, all of the patents, patent applications, articles, and texts which are mentioned above are incorporated herein by reference.
