The present invention relates to the fields of material science and material chemistry, particularly materials and methods to improve corrosion resistance in heat exchangers.
Metal corrosion is a significant problem in the field of material science and material chemistry. Corrosion resistance is a desirable property in metals, particularly those used in aggressive environments conducive to corrosion. One example of such an aggressive environment is seawater. Accordingly, corrosion resistance of metal materials used in marine applications is an acute problem in the field of material science.
The terms “invention,” “the invention,” “this invention” and “the present invention” used herein are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below. Covered embodiments of the invention are defined by the claims, not this summary. This summary is a high-level overview of various aspects of the invention and introduces some of the concepts that are further described in the Detailed Description section below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used in isolation to determine the scope of the claimed subject matter. The subject matter should be understood by reference to appropriate portions of the entire specification, any or all drawings and each claim.
The present invention provides different aluminum (Al) alloy materials which can be used in roll bonding processes to produce plate heat exchangers which contain flow channels or tubes for carrying fluid. These heat exchangers are made with relatively low-cost, roll-bonding processes and display a high heat transfer efficiency and excellent corrosion resistance, particularly in marine environments.
In one process, two separate Al sheets are passed simultaneously through a roll stand, usually at elevated temperature. The upper surface of the lower sheet, which contacts the lower surface of the upper sheet, is usually screen printed with a weld-stop ink in a desired pattern. The appropriate processing temperature for roll bonding will vary as a function of the total gauge reduction and the alloys being processed, but is likely to be somewhere in the range of 150° C. to 500° C. After roll-bonding, a permanent metallurgical bond is created between the two sheets (effectively creating a single sheet). However, the regions of the mating surface incorporating the weld-stop ink do not form a permanent bond. These regions can be separated and the subsequent gap inflated to create integral flow channels suitable for a heat exchanger working fluid (
One Side Clad Material
In one embodiment, the present invention provides a material comprising a corrosion resistant metal alloy core and a metal alloy cladding which is fusion-cast to the metal alloy core to form a one side clad sheet. Fusion casting is known in the art as evidenced in the following U.S. Pat. Nos. 7,748,434, 7,762,310, 7,789,124, 7,882,887, 7,975,752, 8,336,603, 8,347,949, 8,415,025, and 8,418,748.
The metal alloy cladding is selected for ease of roll bonding. In this embodiment the clad layers of two, one side clad sheets are roll bonded to each other to produce an integral tube, twin plate heat exchanger (
Many of the most corrosion resistant alloys contain significant concentrations of magnesium (Mg). This Mg content prevents the use of these alloys in roll-bonding due at least in part to uncontrolled Mg-oxide generation at the roll-bond interface. The central concept is to use a single side clad sheet starting stock in the roll-bonding process. This asymmetric arrangement allows metallurgical bonding at the mating surface to be controlled by the composition of the clad layer. This effectively permits the use of any core alloy in a twin-plate heat exchanger (
In another embodiment, the clad layers of two sheets of a one side clad material are roll bonded together. AA5XXX alloys may be used as the core layer. Generally, AA5XXX alloys which are considered “dilute” or “low in magnesium” are preferred. These alloys are immune to inter-granular corrosion and display good general corrosion resistance. In one embodiment an AA5005 alloy is used. In another embodiment an AA5052 alloy is used. Alloys with magnesium contents in the range 0.5% to 2.7% (weight percent (wt. %) are considered realistic candidates for the above described single-side-clad configuration. In this patent application, all the percentage numbers associated with individual elements in these alloys are expressed in wt. %. The lower limit reflects the minimum needed to provide good marine corrosion resistance, while the upper limit represents the maximum Mg content that can be accommodated without risking sensitization of the microstructure and increased susceptibility to inter-granular corrosion (IGC).
An AA3XXX or AA1XXX alloy can be used for the clad layer. Generally, AA3XXX and AA1XXX alloys which are considered “dilute” or “low in magnesium” are preferred for ease of roll bonding. The wt. % of magnesium in these alloys is generally in the range of 0.01-0.05% for AA1XXX alloys and 0.01-0.2% for AA3XXX alloys. In the one-side-clad configuration described above, the primary purpose of the AA3XXX clad layer or the AA1XXX clad layer is to allow effective roll bonding of the aluminum sheet. A significant consideration for Mg content is the upper limit beyond which Mg oxidation will increase to an extent where effective and consistent roll-bonding cannot occur. Under normal ambient, atmospheric conditions, this limit is probably around 0.2% Mg; although 0.4% Mg could potentially be accommodated if gauge reductions were high enough. If special measures were taken (e.g. inert atmosphere roll-bonding), then it would be theoretically possible to roll bond using clad alloys of >0.4% Mg.
In one embodiment an AA3003 alloy is used for the clad layer. In another embodiment, an AA1100 alloy is used for the clad layer. As long as the Mg content is <0.2% most, if not all, AA1XXX and AA3XXX alloys could be considered for use.
Two Side Clad Material
The present invention also provides a material, comprising a metal core comprising a high content of scrap metal and having two sides, a first metal cladding fusion cast to one side of the core, and a second metal cladding fusion cast to the other side of the core. The material can be in a form of a sheet. Two of these clad sheets are then roll bonded together to produce a permanent metallurgical bond between regions of a clad layer of the first sheet and a clad layer of the second sheet (
In this embodiment, the low cost, but corrosion sensitive core alloy is encapsulated with a corrosion resistant cladding in a manner which prevents contact of the core alloy with either the working fluid (within the integral flow channels), or the external environment (e.g. seawater).
In this embodiment, roll bond friendly alloys are employed for the clad layers. An AA3XXX or AA1XXX alloy can be used for one or both clad layers. In one embodiment both clad layers are AA3XXX. In another embodiment both clad layers are AA1XXX. In yet another embodiment one clad layer is AA1XXX and the other clad layer is AA3XXX. In still another embodiment, one clad layer is AA1XXX or AA3XXX and the other clad layer is AA5XXX. The clad layers may surround a low cost core layer which can contain a relatively high content of scrap metal containing aluminum.
Variable scrap sources can be used to make the core layer so that the heat exchanger panels can act as an effective aluminum scrap sink. The two side clad embodiment resembles a sandwich structure designed to encapsulate virtually any aluminum-based composition in the core layer, whether defined by an AA number or not. In one embodiment, alloy AA4045 was used as the core layer.
An AA3XXX or AA1XXX alloy can be used for one or both clad layers. Generally, AA3XXX and AA1XXX alloys which are considered “dilute” or “low in magnesium” are preferred for ease of roll bonding. The wt % of magnesium in these alloys is generally in the range of 0.01-0.05% for AA1XXX alloys and 0.05-0.2% for AA3XXX alloys. In one embodiment an AA3003 alloy is used for the clad layer. In another embodiment, an AA1100 alloy is used for the clad layer. As long as the Mg content is <0.2% most, if not all, AA1XXX and AA3XXX alloys could be considered for use as the clad layer.
In another embodiment traditional roll cladding can be used as an alternative to fusion casting to produce the clad sheet starting stocks. These clad sheets can then be used in the roll bonding process to produce twin-plate heat exchangers. In this case, all the above mentioned limits on compositions for roll bonding would apply. The most notable limitation would be Mg levels limited to <0.2% (perhaps up to 0.4%, if very high reductions were used).
The aluminum based sheets of the present invention are used to make heat exchangers which possess high corrosion resistance in aqueous environments such as seawater.
Described herein are improved Al-based metal materials that can be described as sheets comprising a core and cladding. In some embodiments the improved metal materials are formed into sheets and the cladding is attached to one side of the sheet (one-sided cladding) or to both sides of the sheet (two-sided cladding). One example of the improved metal material is a one-sided clad sheet comprising a metal alloy core and a metal alloy cladding which is fusion-cast to the metal alloy core. Another example of the improved metal material is a sheet comprising a metal core with first metal cladding fusion-cast to the first side of the core, and a second cladding fusion-cast to the second side of the core. Still another example of the improved metal material is a sheet comprising a metal alloy core and a metal alloy cladding which is roll-bonded to the metal alloy core. Yet another example of the improved metal material is a sheet comprising a metal core with first metal cladding roll-bonded to the first side of the core, and a second cladding roll-bonded to the second side of the core. Embodiments of the improved metal materials described herein can be referred to as “clad sheet alloys.”
The inventors discovered that, by combining different metal alloys in the clad sheet alloys, they can achieve one or more of the following advantages: improved ease of fabrication of the metal composites; lowered fabrication costs due to use of scrap in the core layer; increased corrosion resistance; and, incorporation of high scrap metal content. Two clear advantages of the Fusion/Roll bonding combination are corrosion resistance (by virtue of being able to use corrosion resistant alloys that would not normally be roll bondable) and scrap incorporation into the core layer which is not possible in a monolithic form.
Also described herein are processes for preparing the above improved metal materials and forms fabricated from these materials.
Corrosion Resistance
Corrosion resistance of metal materials is an acute problem in the field of material science, particularly when the materials are used in aggressive environments. One example of an aggressive environment is a marine environment. Some metals, such as aluminum, which are typically corrosion resistant under normal conditions, are still prone to corrosion in the marine environment. Aluminum can be very easily oxidized, forming a protective passive oxide film on the metal surface. Formation of a stable oxide film on the aluminum surface generally provides excellent resistance to corrosion. Corrosion of aluminum can take place, however, when the oxide film is damaged or under certain electrochemical conditions, including the presence of chloride anions, such as in seawater. Pitting corrosion is a form of highly localized corrosion occurring on a metal surface, which is often observed to initiate at weak points in the passive film, such as intermetallic inclusions or particles. Once the passive film at local points is broken, ion/electron pairs are created and corrosion is able to proceed by half reactions occurring at the anodic and cathodic sites. Pitting resistance can be evaluated by electrochemical testing methods, such as linear polarization experiments.
Some aluminum alloys possess higher pitting resistance than the other alloys and are therefore more corrosion resistant when used in the aggressive environments, such as seawater. However, such corrosion resistant alloys may be expensive to produce, and also do not necessarily possess physical properties that allow them to be exploited in certain applications or technological processes. For example, some of the available corrosion resistant aluminum alloys cannot be easily processed by roll-bonding.
Clad Sheet Alloys
Roll-bonding is a cost-efficient fabrication technique highly useful for production of certain composite metals, materials forms and objects. The inventors discovered that it is possible to utilize the advantages of roll-bonding of an aluminum material, yet achieve higher corrosion resistance than allowed by the alloys usually suitable for roll-bonding. This objective can be accomplished by combining the alloys suitable for roll-bonding with corrosion resistant alloys in the same materials. In one particular example, metal sheets and other related forms can be produced that incorporate both aluminum alloys suitable for roll-bonding and highly corrosion resistant alloys.
Sheets and other forms of the materials described herein can be referred to as “clad sheet materials,” “clad sheet alloys” and by other related terms. Clad sheet alloys or materials described herein typically incorporate a core of a corrosion resistant alloy and at least one cladding layer for ease in roll bonding (
Core
Some embodiments of the clad sheet alloys described herein contain a core aluminum alloy compatible with conventional roll-bonding processes. In addition, core alloys may be selected for one or more of the following characteristics: formability; corrosion resistance, such as long term corrosion resistance in warm and cold seawater; suitable galvanic balance between core alloy and cladding alloy to ensure self-protection of the clad sheet alloy at the edges exposed to a corrosive environment; compatibility with re-melting; and, conventional rolling processes.
Roll-bonding compatible aluminum alloys contain various elements as shown in the table below.
A significant consideration for Mg content is the upper limit beyond which Mg oxidation will increase to an extent where effective and consistent roll-bonding cannot occur. Under normal ambient, atmospheric conditions, this limit is probably around 0.2% Mg; although 0.4% Mg could potentially be accommodated if gauge reductions were high enough. If special measures were taken (e.g. inert atmosphere roll-bonding), then it would be theoretically possible to roll bond using clad alloys of >0.4% Mg. Generally, alloys containing <0.2% Mg are candidates for roll bonding.
Composition of some roll-bonding compatible alloys (weight percent (wt %))
Some other embodiments the clad sheet alloys described herein contain a core aluminum alloy with high scrap metal content.
Cladding
Clad sheet alloys described herein contain cladding on one or both sides of the sheet. The alloys used for cladding, or “cladding alloys” are aluminum alloys. Some of the cladding alloys are selected for corrosion resistance. For example, in some embodiments, cladding alloys are selected for high corrosion resistance or for ease of roll bonding or both. For example, cladding alloys may be selected to exhibit long term corrosion resistance in warm and cold seawater. Some other factors used for selection of the cladding alloys are one or more of the following: compatibility with roll bonding; compatibility with fusion casting; formability; corrosion resistance, such as long term corrosion resistance in warm and cold seawater; suitable galvanic balance between core alloy and cladding alloy to ensure self-protection of the clad sheet alloy at the edges exposed to a corrosive environment; compatibility with re-melting; and, conventional rolling processes.
In this embodiment, desirable clad compositions are roll bonding compatible (i.e. very low Mg) but still possess good marine corrosion resistance. In such a case, higher purity base compositions (minimizing Fe, Cu, Mn and other common background impurities) may be used. This is because these elements typically reside as cathodic second phase constituents in the alloy matrix. As such, they tend to promote micro-galvanic activity in chloride bearing media and consequent passive film breakdown and pitting corrosion. Accordingly, alloys such as AA1050, AA1060, AA1070 (or even purer AA1080) might be preferred. For 3XXX, higher purity base compositions such as AA3003, AA3004 and AA3104 may be used.
Clad Sheet Alloy Embodiments
One-Sided Clad Sheet
One exemplary embodiment of the clad sheet is a one-sided clad sheet alloy. A one-sided clad sheet alloy includes a clad of an aluminum alloy selected for compatibility with roll bonding and a one sided core of an aluminum alloy selected on the basis of maximum resistance to pitting corrosion in an aggressive environment, such as a marine environment. It is important to note that typical aluminum alloys suitable for marine environments due to their high corrosion resistance cannot be roll-bonded due to the presence of Mg based thermal oxides in such alloys. In one embodiment, the cladding is applied by fusion casting technology, followed by hot rolling and cold rolling into sheets. In another embodiment, a clad layer is applied to a core layer through conventional roll bonding techniques.
An aluminum panel comprised of one-sided clad sheet was roll bonded to a second one-sided clad sheet, with the two clad layers facing each other, in order to produce an integral tube, twin-plate heat exchanger. A one side clad sheet comprised a corrosion resistant core alloy and a clad alloy was selected for the ease of roll bonding (
Two separate aluminum sheets are passed simultaneously through a roll stand, usually at an elevated temperature (
In one embodiment, the present invention provides a material comprising a corrosion resistant metal alloy core and a metal alloy cladding which is fusion-cast to the metal alloy core. The metal alloy cladding is selected for ease of roll bonding. In this embodiment two, one-sided clad sheets are roll bonded to each other to produce an integral tube, twin plate heat exchanger (
In one embodiment, two sheets of a one-sided clad material are employed and are roll bonded together. AA5XXX alloys may be used as the core layer. Generally, AA5XXX alloys which are considered “dilute” or “low in magnesium” are preferred. These alloys are relatively immune to intergranular corrosion and display good corrosion resistance. In one embodiment a AA5005 alloy is used. In another embodiment a AA5052 alloy is used.
An AA3XXX or AA1XXX alloy can be used for the clad layer. Generally, AA3XXX and AA1XXX alloys which are considered “dilute” or “low in magnesium” are preferred for ease of roll bonding. The wt % of magnesium in these alloys is generally in the range of 0.01-0.05% for AA1XXX alloys and 0.05-0.2% for AA3XXX alloys. In one embodiment an AA3003 alloy is used for the clad layer. In another embodiment, an AA1100 alloy is used for the clad layer. As long as the Mg content is <0.2% most, if not all, AA1XXX and AA3XXX alloys could be considered for use as the clad layer.
Two-Sided Clad Sheet
Another embodiment of the clad sheet alloys of the invention is a two-sided clad sheet alloy (
The present invention also provides a material comprising a metal core comprising a high content of scrap metal and having two sides, a first metal cladding fusion cast to one side of the core, and a second metal cladding fusion cast to the other side of the core. The material can be in a form of a sheet. Two of these clad sheets are then roll bonded together to produce a permanent metallurgical bond between regions of a clad layer of the first sheet and a clad layer of the second sheet.
In this embodiment, the low cost, but corrosion sensitive core alloy is encapsulated with a corrosion resistant cladding in a manner which prevents contact of the core alloy with either the working fluid (within the integral flow channels), or the external environment (e.g. seawater).
In this embodiment, roll bond friendly alloys are employed. An AA3XXX or AA1XXX alloy can be used for one or both clad layers. In one embodiment both clad layers are AA3XXX. In another embodiment both clad layers are AA1XXX. In yet another embodiment one clad layer is AA1XXX and the other clad layer is AA3XXX. In still another embodiment, one clad layer is AA1XXX or AA3XXX and the other clad layer is AA5XXX.
The clad layers may surround a low cost core layer which can contain a relatively high content of scrap metal containing aluminum.
In one embodiment, the core alloy is an AA4045 alloy as shown above. The definition of scrap metal means that it contains higher Si, Fe, Cu and Zn elements.
A AA3XXX or AA1XXX alloy can be used for one or both clad layers. Generally, AA3XXX and AA1XXX alloys which are considered “dilute” or “low in magnesium” are preferred for ease of roll bonding. As long as the Mg content is <0.2% most if not all AA1XXX and AA3XXX alloys could be considered for use as the clad layer. The weight percent (wt %) of magnesium in these alloys is generally in the range of 0.01-0.05 for AA1XXX alloys and 0.05-0.2 for AA3XXX alloys. In one embodiment an AA3003 alloy is used for the clad layer. In another embodiment, an AA1100 alloy is used for the clad layer.
Processes for Making Corrosion Resistant Heat Exchanger
The clad sheet alloys described herein can be fabricated by the processes that include at least some of the technologies described herein. The processes for fabricating cast sheet alloys are included within the scope of the present invention.
Two separate Al sheets are passed simultaneously through a roll stand (usually at elevated temperature) (
Roll bonding temperature ranges will be from about 150° C. to 500° C. depending on the alloys/gauges and total reductions being used, as known to one of ordinary skill in the art. The maximum inflation height will depend on the design requirement and the warm/hot forming characteristics of the alloy(s) being roll bonded; especially the maximum elongation of the alloy strip.
Clad sheet alloys described herein can be used in a variety of applications. One exemplary application fabrication of aluminum panel heat exchanger models for power plants. More generally, clad sheet alloys with high corrosion resistance cladding are suitable for various uses in marine environments. These clad sheet alloys can be used to extract useful energy from relatively low grade heat waste such as the warm water found in the upper ocean, or from other waste heat flows for example discharges from power plants, or discharges associated with other industrial processes.
The clad sheet alloys described herein can possess various structural and functional characteristics and properties. These characteristics and properties can be used for descriptive and distinguishing purposes, but can also be advantageously employed in various uses and applications of the combination coatings described herein. Some, but not all, of the characteristics and properties of the films and coatings are ease and lower cost of fabrication, which may be achieved, for example, by utilizing roll bonding technology and/or scrap metal and excellent corrosion resistance. Embodiment of the clad sheet alloys suitable for specific applications can possessed some application-specific characteristics.
Objects, forms, apparatuses and similar things fabricated or comprising clad sheet alloys are included within the scope of the present invention. One exemplary object is a heat exchanger.
The following examples will serve to further illustrate the present invention without, at the same time, however, constituting any limitation thereof. On the contrary, it is to be clearly understood that resort may be had to various embodiments, modifications and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the invention. During the studies described in the following examples, conventional procedures were followed, unless otherwise stated. Some of the procedures are described below for illustrative purpose.
An ingot comprising an AA5005A core and an AA3003 clad was cast in a 1900 mm wide mold. The ingot was about 12,000 Kg with 10% (wt %) clad. The core surface was scalped approximately 12 mm. The liner surface was scalped approximately 11 mm. The ingot was center split to enhance efficiency of production. The scalped ingot was run through a reversing mill with the liner 3003 on the bottom surface at the hotline and on the top surface at the cold and finish line. Two edge cuts were made. The cold ingot was run through a reversing mill after cropping, and then on to a finishing mill. A ground work roll with a particular grind was used to indicate the clad surface of the sheet.
An aluminum panel comprised of one-side-clad sheet produced as in Example 1 was roll bonded to a second one-side-clad sheet produced as in Example 1, with the two clad layers facing each other, in order to produce an integral tube, twin-plate heat exchanger.
Many of the most corrosion resistant alloys contain significant concentrations of magnesium. This magnesium content prevents the use of these alloys and roll bonding relating to uncontrolled magnesium oxide generation of the roll bonded interface. In this embodiment a single side clad sheet was used as starting stock in the roll bonding process. This asymmetric arrangement allows metallurgical bonding at the meeting surface to be controlled by the composition of the clad layer. This effectively permits the use of any core alloy in a twin plate heat exchanger.
Two separate aluminum sheets are passed simultaneously through a roll stand, usually at an elevated temperature (
In this example, an aluminum panel comprised of a two-side-clad sheet is roll bonded to another two-side-clad sheet to put producing integral tube, twin plate heat exchanger. The clad upper surface of the lower sheet is usually screen-printed with a weld-stop ink in a desired pattern. In this embodiment the two-sided clad sheet is comprised of corrosion resistant clad alloy and a low-cost, high scrap core. An integral flow channel for the working fluid is created between the upper and the lower sheet by applying pressure to the areas screen-printed with a weld-stop ink. Depending on the alloys being used and the overall gauges, inflation of the channels can be achieved by techniques known to one of ordinary skill in the art, such as compressed air, or hydraulic fluid (if higher pressures are needed). A cross-section through the joint region between the upper and lower fusion sheets using roll bonding shows a permanent metallic bond. In this manner the corrosion sensitive core alloy which contains scrap at lower cost is encapsulated with a corrosion resistant cladding in a manner that prevents contact with either the working fluid (within the integral flow channels), or the external environment (e.g., seawater).
All patents, publications and abstracts cited above are incorporated herein by reference in their entirety. Different arrangements and combinations of the elements and the features described herein are possible. Similarly, some features and sub combinations are useful and may be employed without reference to other features and sub combinations. Various embodiments of the invention have been described in fulfillment of the various objectives of the invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.
This application claims the benefit of U.S. Provisional Application No. 62/095,146, filed Dec. 22, 2014, which is hereby incorporated herein by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/US2015/065667 | 12/15/2015 | WO | 00 |
Number | Date | Country | |
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62095146 | Dec 2014 | US |