The present invention relates to brazing sheet materials, heat exchangers, methods for making same and more particularly, to multi-layer aluminum alloy brazing sheet that is formed by roll bonding.
Roll-bonded, multi-layer brazing sheet materials are known wherein multiple layers of different aluminum alloys, e.g., for forming a core, a braze liner and an interliner, are stacked and passed through a rolling mill. Typically, the stack of layers is pre-heated and the rolling mill exerts high pressure on the stack, causing the stack to be reduced in cumulative thickness, as well as reducing the thickness of the individual layers. The rolling process and reduction in thickness also cause the individual layers to bond to one another, yielding a single composite sheet of reduced thickness with a plurality of layers. An interliner/interliner layer may be used in a multi-layer brazing sheet to reduce migration of elements, e.g., between the core and the braze liner during brazing that leads to diminished corrosion resistance. Under a low pH environment such as an EGR (exhaust gas recirculation) related CAC (charge air cooler), the core materials can be easily susceptible to corrosion such as intergranular corrosion without the protection of interliners. Known interliners, such as alloy 0140 available from Arconic, Inc. of Pittsburgh, Pa., U.S.A. or AA1145, sometimes exhibit difficulty in bonding to adjacent layers when roll bonded to form a laminate. Notwithstanding known methods, materials and apparatus, alternative methods, apparatus and materials for making multi-layer, roll-bonded brazing heat material remain desirable.
The disclosed subject matter relates to a multi-layer sheet material, having:
core of one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy; a braze liner of 4XXX aluminum alloy; and an interliner having a composition of: 0.31-1.0 wt. % Si, <0.1 wt. % Mg, 0.25-1.0 wt. % Mn, up to 5.0 wt. % Zn, up to 0.3 wt. % Fe, up to 0.2 wt. % Cu, up to 0.125 wt. % Zr, other elements ≤0.05 wt. % each and ≤0.15 wt. % total, balance Al.
In another embodiment, the interliner contains 0.34-0.5 wt. % Si, <0.05 wt. % Mg and 0.25-0.35 wt. % Mn, ≤0.05 wt. % Zn, ≤0.3 wt. % Fe, ≤0.05 wt. % Cu.
In another embodiment, the interliner is disposed between the braze liner and the core.
In another embodiment, the interliner contains 0.4-0.5 wt. % Si.
In another embodiment, the interliner contains 0.25-0.34 wt. % Mn
In another embodiment, the interliner further comprises 0.05-5.0 wt. % Zn.
In another embodiment, an increase in flow stress in the interliner attributable to the presence of at least one of Mg and Mn is in the range of 20% to 52% over the flow stress in the interliner without the presence of at least one of Mg and Mn.
In another embodiment, the core is a 3003 aluminum alloy.
In another embodiment, the core comprises 0.1 to 1.0 wt. % Si; up to 0.5 wt. % Fe, 0.2 to 1.0 wt. % Cu; 1.0 to 1.5 wt. % Mn, 0.2 to 0.3 wt. % Mg; up to 0.05 wt. % Zn and 0.1 to 0.2 wt. % Ti.
In another embodiment, the braze liner comprises: 6.8 to 8.2 wt. % Si; up to 0.8 wt. % Fe, up to 0.25 wt. % Cu; up to 0.1 wt. % Mn and up to 0.2 wt. % Zn.
In another embodiment, further including another liner disposed on the core distal to the interliner and the braze liner.
In another embodiment, the another liner includes a second braze liner and a second interliner, the second interliner disposed between the core and the second braze liner.
In another embodiment, the interliner contains 0.34 to 0.5 wt. % Si, up to 0.1 wt. % Zn and further comprises up to 0.3 wt. % Fe and up to 0.2 wt. % Cu, balance Al and other elements <0.05 wt. % each, 0.15 wt. % total.
In another embodiment, the interliner contains <0.05 wt. % Cu and further comprising up to 0.125 wt. % Zr.
In another embodiment, the sheet material has a total thickness of from 0.1 mm to 3.0 mm with a core thickness of 0.09 mm to 2.85 mm, the braze liner having a clad ratio of 2.5% to 20% and the interliner having a clad ratio of 2.5 to 20%.
In another embodiment, the sheet material is O temper.
In another embodiment, a heat exchanger has at least one of a tube, a fin, a header plate or a tank with a sheet material having core of one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy; a braze liner of 4XXX aluminum alloy; and an interliner having a composition of: 0.31-1.0 wt. % Si, <0.1 wt. % Mg, 0.25-1.0 wt. % Mn, other elements ≤0.05 wt. % each and ≤0.15 wt. % total, balance Al.
In another embodiment, a multi-layer sheet material, has a core of one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy; a braze liner of 4XXX aluminum alloy; and
an interliner with 0.31-1.0 wt. % Si, 0.1-0.5 wt. % Mg, 0.05-0.3 wt. % Mn, up to 5.0 Wt. % Zn, other elements ≤0.05 wt. % each and ≤0.15 wt. % total, balance Al.
In another embodiment, the interliner contains 0.05-5.0 wt. % Zn.
In another embodiment, a method for making a brazing sheet includes the steps of:
providing a layer of interliner comprising 0.31-1.0 wt. % Si; <0.1 wt. % Mg; 0.25-1.0 wt. % Mn; providing a layer of core material selected from one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy; providing a layer of braze liner material of 4XXX aluminum alloy; stacking the layer of interliner, the layer of core material and the layer of braze liner material into a stack with the interliner disposed between the layer of core material and the layer of braze liner material; and rolling the stack to form a bonded multi-layer brazing sheet.
For a more complete understanding of the present disclosure, reference is made to the following detailed description of exemplary embodiments considered in conjunction with the accompanying drawings.
An aspect of the present disclosure is the recognition that brazing sheet has several objectives, e.g., light weight, high strength and corrosion resistance and further that these attributes often are conflicting. For example, the use of 3XXX aluminum alloys for core layers of a brazing sheet contributes to the overall strength of the sheet material after brazing, but typical 4XXX braze liner will cause severe liquid film migration (LFM) upon brazing, leading to reduced corrosion resistance. This is particularly true with respect to O temper braze sheet (or brazing sheet) using 3XXX core and 4XXX braze liner (also known as a braze layer). Interliners (also known as an interlayer or interliner layer) made from high purity aluminum alloys, such as, Arconic alloy 0140, and AA1145 may be used as a protection layer, resulting in improved corrosion resistance, but such interliner materials sometimes result in roll bonding deficiencies, giving rise to delamination in whole or part (blistering) of the core and brazing layer at the interliner interface.
An aspect of the present disclosure is the recognition that high purity interliner alloys are soft, in particular, relative to core alloys, e.g., in the 2XXX, 3XXX, 5XXX and 6XXX alloy series, such as 3003 aluminum alloy, and/or 4XXX brazing alloys, such as 4047, 4045, 4343, 4147, 4004, 4104 alloys and derivatives of these alloys with zinc additions. Typical rolling temperature for multi-layer brazing products has a range between 700 to 1000° F. which can vary based on specific manufacturing processes and materials to be rolled. During rolling at this temperature range, large differences in flow stress of these alloys can cause materials to deform distinctly which presents challenges to forming bonded products. Flow stresses of these layers at the rolling temperature defines their mechanical behavior and are relevant to the rolling behavior and bondability.
An aspect of the present disclosure is the recognition that a smaller difference in flow stress of the various layers of a roll-bonded multi-layer sheet, e.g., the interliner relative to the core and/or braze liner, may give rise to better bonding between the multiple layers and that if the flow stress of layers of a multi-layer, roll bonded sheet are closer in value, the bonding produced by roll-bonding the multi-layer sheet will be facilitated. The term “bondability” may be used to designate the property of adjacent layers to be bonded together by roll bonding. For example, adjacent sheets that have higher bondability would more readily and/or more successfully bond to one another when roll bonded compared to adjacent sheets that have lower bondability.
An aspect of the present application is the recognition that the flow stress of a relatively soft layer in a multi-layer roll-bonded brazing sheet may be adjusted by adding elements that strengthen the soft layer to more closely approach the flow stress of other layers to which it is bonded and that this adjustment of hardness will improve the bondability of the previously softer layer.
An aspect of the present disclosure is the recognition that the strengthening of a soft layer in a multi-layer, roll-bonded brazing sheet will result in an increase in the flow stress. Further, that roll bonding is promoted when the flow stress of adjacent layers is closer in value to one another. With respect to an interliner layer made from, e.g., Arconic alloy 0140 (See Table 2, IL0), this alloy can be observed to have a flow stress of 1.25, 1.91 and 3.15 ksi at strain rates of 0.01. 0.1 and 1/second respectively at 900° F. (See Table 4 below). By comparison, the flow stress of a 3XXX core alloy, such as, 3003 has a flow stress of 2.09, 3.19, and 5.16 ksi at strain rates of 0.01. 0.1 and 1/second, respectively; a 4XXX brazing liner, such as, 4343 has as flow stress of 1.7, 2.62, and 4.55 ksi at strain rates of 0.01. 0.1 and 1/second, respectively (Table 4). By adding 0.2 to 0.3 wt. % of Mn to 0140 aluminum alloy (IL4, IL5, and IL6 of Table 2) , the flow stress can be increased to 1.72, 2.35 and 3.78 ksi to 1.9, 2.6 and 3.87 ksi for 0.01. 0.1 and 1/second, respectively, representing an increase in flow stress of between 20% and 52%. Further addition of 0.1 to 0.4 wt. % Mg to 0140 aluminum alloy (IL7, IL8 and IL10 alloy in Table 4) can increase the flow stress of the resultant alloys to higher levels. Good roll-bonding for multiple aluminum alloy layers requires breaking all surface aluminum oxides simultaneously so the aluminum underneath can bond metallurgically. When a softer interliner is used to make a multi-layer material, it can be deformed more easily, but both the harder braze liner and core alloy will have a relatively lower amount of deformation. The lower deformation of the braze liner and core is less effective in breaking down the surface oxides, making a good metallurgical bond with the interliner harder to form. In accordance with the present disclosure, to promote good bonding, a smaller difference in flow stress between layers is preferred. A closer matching of flow stresses between the interliner and the braze liner is beneficial for roll-bonding and helps to prevent blisters that are often found between the braze liner and interliner alloys in multi-layer braze sheets.
The brazing sheet material 10 has a range of thicknesses from 0.1 to 3 mm, with the core having a thickness of 0.1 to 2.85 mm, the braze liner a thickness of 0.005 to 0.6 mm or a clad ratio of 2.5 to 20% and the interliner a thickness from 0.005 to 0.6 mm (a clad ratio of 2.5 to 20%).
In another embodiment, 0.10-0.5 wt. % Mg with or potentially without a small amount of Mn, i.e., from 0.05 to 0.3 wt. % can provide a beneficial effect similar to the presence of 0.25-1.0 wt. % Mn, as described above.
In another embodiment, an addition of up to 5 wt. % zinc can be added to an interliner alloy in accordance with the present disclosure to aid corrosion resistance without changing the flow stress and LFM behavior for the braze liner and interliners alloys herein. In one example, the internal environment I may be exhaust gas from in internal combustion engine and the outer environment O may be air or coolant.
An aspect of the present disclosure is the recognition that when an interliner is used in a brazing sheet with a high strength aluminum alloy, such as a 3XXX series alloy, the interliner tends to experience significant liquid film migration (LFM) during brazing, which can negatively affect corrosion resistance. This is particularly true of O temper materials. Brazing sheet is often supplied in O temper, i.e., after full annealing. O temper brazing sheet exhibits good formability that permits the sheet to be formed into the necessary shapes required for making components, such as EGR type CACs (charge air coolers) and heat exchanger parts, e.g., tubes, end plates, manifolds, collector tanks, etc. It is critical to maintain corrosion protection functions for the interliners when components made of these multilayer materials are exposed to corrosive environments. By forming multilayer sheet material, where O temper is preferred, the forming process may create residual strains in the materials in their formed shapes. It is known that O temper, multilayer brazing sheet with a 3XXX interliner with low residual strain (i.e. <10%) can experience severe LFM during brazing by reacting with brazing filler materials. For this reason, high purity interliner alloys such as 0140 were preferred as they recrystallize early during the brazing cycle and LFM can be prevented. An aspect of the present disclosure is the identification of strengthening elements and their concentration limits to achieve a higher flow stress for improved roll-bonding and also have a much less significant LFM impact on corrosion resistance than, e.g., 3XXX alloy interliners. A further aspect of the present disclosure is to minimize LFM without diminishing corrosion resistance, while at the same time achieving improved roll-bondability. An interliner 16 in accordance with the present disclosure promotes roll bonding while preserving good resistance to LFM, corrosion resistance and brazeability via the braze liner 14. If the interliner 16 were to include strengthening elements such as Mn in excess of 0.34 wt. %, and experience a small amount of strain from a forming process prior to brazing, LFM can change the microstructure and chemical composition of the interliner layer. This is in general not preferred for brazed heat exchanger or other components and is illustrated by IL8 shown in
The brazing sheet material 10 shown in
Various examples of cores, interliners and braze liner having various compositions were prepared. The compositions of the core alloys are shown in Table 1, the compositions for the interliner are shown in Table 2, and the braze liner compositions are shown in Table 3. The alloys identified as “0359” (Table 1) and “0611” (Table 2) are alloys sold by Arconic, Inc. of Pittsburg, Pa., U.S.A.
In each of the compositions for the core, braze liners and interliners disclosed herein, the composition is an aluminum alloy expressed in weight percent of each listed element with aluminum and impurities as the remainder of the composition, i.e., other element ≤0.05 each and ≤0.15 wt. % total. The compositional ranges of the elements include all intermediate values as if expressed literally herein. For example, in the above composition, Mn in the range of 0.1 to 0.3 wt. % includes, 0.01, 0.02, 0.03, 0.04 . . . , 0.28, 0.29 and 0.30 wt. % and all intermediate values, such as: 0.11, 0.24 wt. %, etc., in increments of 0.01 wt. %.
The fabrication practice includes, but is not limited to, casting the ingots of the high strength core alloy, the 4XXX braze liner alloy and the interliner alloy of the 3-layer architecture shown in
In some embodiments, the stack-up/composite consists of 3 layers that are subjected to a reheat process for hot rolling. The hot rolling temperature has a range of 400° C.-520° C.
In some embodiments, the resultant multilayer composite is cold rolled to an intermediate gauge and then goes through an intermediate anneal at a temperature range of 340° C.-420° C. and soak time up to 8 hours. After intermediate annealing, the composite is again cold rolled to a lighter gauge or a final gauge of 0.1 to 3 mm. In some embodiments, the material may be subjected to more than one intermediate anneal and then rolled to a lighter gauge and then another intermediate anneal. In some embodiments, the material at the final gauge is subject to a final partial anneal or a full anneal in a temperature range of 150° C.-420° C. and a soak time up to 8 hours.
In some embodiments, the composite is cold rolled directly to a final gauge without an intermediate anneal and then subjected to a final partial anneal or a full anneal in a temperature range of 150° C. to 420° C. and soak time up to 8 hours.
With added strengthening elements such as Mn, Mg, Cu and Zr, a series of experimental interliner alloys (listed in Table 2) were cast into ingots of dimensions 14″ by 10″ by 2″. Cylindrical coupons (10 mm in diameter and 15 mm long) were prepared from the ingot material after a pre-heat treatment. These coupons were measured for their flow stress at a representative rolling temperature. Core alloys, braze liner 4343 and the base line high purity interliner (IL0) were also measured for comparison. The composition of the core alloys and braze liner are listed in Table 1 and Table 3 above, respectively. In accordance with an aspect of the present disclosure, a smaller difference in flow stress at rolling temperature between these layers promotes roll-bonding especially for the soft interliner layers. Flow stress testing was carried out with a Gleeble thermomechanical Simulator. The tests were done at a temperature of 900° F. (482° C.), which is representative for rolling temperature range (400 to 520° C.) for multilayer brazing sheets. Three strain rates were applied for the flow stress measurements: 0.01, 0.1 and 1/second. These strain rates were selected to cover a wide range of typical reduction for the rolling operation of brazing sheets. Table 4 below lists the flow stress of the relevant alloys at 900° F. measured with stain rates at 0.01. 0.1 and 1/sec, respectively. The flow stress value at each stain rate was calculated by averaging the values between 0.2 to 0.7 true strain from a compression test with the Gleeble thermomechanical simulator.
The results recorded in Table 4 are shown in
During roll-bonding, a high purity interliner such as IL0 (0140 alloy) will deform more easily compared to braze layers, such as 4343 (alloy B) and core alloys, such as 3003/0359 (Core alloy A and B), which can often cause delamination, blistering and curvature of multi-layer ingot/plate assemblies. The measured flow stresses of a high purity interliner (IL0, 0140) alloy and a braze liner 4343 and 3003/0359 (Core A and B) are shown in the
The corrosion test used to assess the interliner alloys of Table 2 used a solution that was a mixture of sulfuric, nitric, formic and acetic acids with a pH of 2.4 and 50 mg/L sodium chloride. The solution was to simulate an exhaust gas recirculation (EGR) type of environment. Alternating dry (16 hours in the air) and wet (8 hours in the solution) cycles were used for this test method and aeration was applied into the solution for the wet cycle to accelerate the corrosion.
As shown in
The present disclosure utilizes standard abbreviations for the elements that appear in the periodic table of elements, e.g., Mg (magnesium), O (oxygen), Si (silicon), Al (aluminum), Bi (bismuth), Fe (iron), Zn (zinc), Cu (copper), Mn (manganese), Ti (titanium), Zr (zirconium), F (fluorine), K (potassium), Cs (Cesium), etc.
The figures constitute a part of this specification and include illustrative embodiments of the present disclosure and illustrate various objects and features thereof. In addition, any measurements, specifications and the like shown in the figures are intended to be illustrative, and not restrictive. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the invention that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the invention is intended to be illustrative, and not restrictive.
Throughout the specification and claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrases “in one embodiment” and “in some embodiments” as used herein do not necessarily refer to the same embodiment(s), though it may. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to a different embodiment, although it may. Thus, as described below, various embodiments of the invention may be readily combined, without departing from the scope or spirit of the invention.
In addition, as used herein, the term “or” is an inclusive “or” operator, and is equivalent to the term “and/or,” unless the context clearly dictates otherwise. The term “based on” is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In addition, throughout the specification, the meaning of “a,” “an,” and “the” include plural references. The meaning of “in” includes “in” and “on”.
Aspects of the invention will now be described with reference to the following numbered clauses:
1. A multi-layer sheet material, comprising:
a core of one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy;
a braze liner of 4XXX aluminum alloy; and
an interliner comprising:
0.31-1.0 wt. % Si;
<0.1 wt. % Mg;
0.25-1.0 wt. % Mn;
up to 5.0 wt. % Zn;
up to 0.3 wt. % Fe;
up to 0.2 wt. % Cu;
up to 0.125 wt. % Zr;
other elements ≤0.05 wt. % each and ≤0.15 wt. % total, balance Al.
2. The sheet material of Clause 1, wherein the interliner contains
0.34-0.5 wt. % Si;
<0.05 wt. % Mg;
0.25-0.35 wt. % Mn
≤0.05 wt. % Zn;
≤0.05 wt. % Cu.
3. The sheet material of Clause 1 or Clause 2, wherein the interliner is disposed between the braze liner and the core.
4. The sheet material of Clause 2 or Clause 3, wherein the interliner contains 0.4-0.5 wt. % Si.
5. The sheet material of any of Clauses 2-4, wherein the interliner contains 0.25-0.34 wt. % Mn 6. The sheet material of any of Clauses 1-5, wherein the interliner further comprises 0.05-5.0 wt. % Zn.
7. The sheet material of any of Clauses 1-6, wherein an increase in flow stress in the interliner attributable to the presence of at least one of Mg and Mn is in the range of 20% to 52% over the flow stress in the interliner without the presence of at least one of Mg and Mn.
8. The sheet material of any of Clauses 1-7, wherein the core is a 3003 aluminum alloy.
9. The sheet material of any of Clauses 1-7, wherein the core comprises 0.1 to 1.0 wt. % Si; up to 0.5 wt. % Fe, 0.2 to 1.0 wt. % Cu; 1.0 to 1.5 wt. % Mn, 0.2 to 0.3 wt. % Mg; up to 0.05 wt. % Zn and 0.1 to 0.2 wt. % Ti.
10. The sheet material of any of Clauses 1-9, wherein the braze liner comprises: 6.8 to 8.2 wt. % Si; up to 0.8 wt. % Fe, up to 0.25 wt. % Cu; up to 0.1 wt. % Mn and up to 0.2 wt. % Zn.
11. The sheet material of any of Clauses 1-10, further comprising another liner disposed on the core distal to the interliner and the braze liner.
12. The sheet material of Clause 11, wherein the another liner includes a second braze liner and a second interliner, the second interliner disposed between the core and the second braze liner.
13. The sheet material of Clause 1, wherein the interliner contains 0.34 to 0.5 wt. % Si and up to 0.1 wt. % Zn.
14. The sheet material of Clause 13, wherein the interliner contains <0.05 wt. % Cu.
15. The sheet material of any of Clauses 1-14, wherein the sheet material has a total thickness of from 0.1 mm to 3.0 mm with a core thickness of 0.09 mm to 2.85 mm, the braze liner having a clad ratio of 2.5% to 20% and the interliner having a clad ratio of 2.5 to 20%.
16. The sheet material of any of Clauses 1-15, wherein the sheet material is O temper.
17. A heat exchanger, comprising at least one of a tube, a fin, a header plate or a tank comprising the sheet material of any of Clauses 1-16.
18. A multi-layer sheet material, comprising:
a core of one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy;
a braze liner of 4XXX aluminum alloy; and
an interliner comprising:
0.31-1.0 wt. % Si;
0.1-0.5 wt. % Mg;
0.05-0.3 wt. % Mn;
up to 5.0 Wt. % Zn;
other elements ≤0.05 wt. % each and ≤0.15 wt. % total, balance Al.
19. The sheet material of Clause 18, wherein the interliner contains 0.05-5.0 wt. % Zn.
20. A method for making a brazing sheet comprising the steps of:
providing a layer of interliner comprising 0.31-1.0 wt. % Si; <0.1 wt. % Mg; 0.25-1.0 wt. % Mn;
providing a layer of core material selected from one of 2XXX, 3XXX, 5XXX or 6XXX aluminum alloy;
providing a layer of braze liner material of 4XXX aluminum alloy;
stacking the layer of interliner, the layer of core material and the layer of braze liner material into a stack with the interliner disposed between the layer of core material and the layer of braze liner material; and
rolling the stack to form a bonded multi-layer brazing sheet.
While a number of embodiments of the present invention have been described, it is understood that these embodiments are illustrative only, and not restrictive, and that many modifications may become apparent to those of ordinary skill in the art. Further still, the various steps may be carried out in any desired order (and any desired steps may be added and/or any desired steps may be eliminated. All such variations and modifications are intended to be included within the scope of the appended claims.
Filing Document | Filing Date | Country | Kind |
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PCT/US2019/028824 | 4/24/2019 | WO | 00 |