ALUMINUM BRAZING SHEET FOR FLUX-FREE BRAZING

Abstract

An aluminum brazing sheet has a multilayer structure of two or more layers of at least a core material and a brazing material, wherein an Al—Si—Mg—Bi-based brazing material containing, by mass %, 0.01% to 2.0% of Mg, 1.5% to 14.0% of Si, and 0.005% to 1.5% of Bi is clad on one surface or both surfaces of the core material to be located at an outermost surface of the aluminum brazing sheet, in the Al—Si—Mg—Bi based brazing material, there are more than 10 Mg—Bi-based compounds having a diameter of 0.01 μm or more and less than 5.0 μm when observed in a surface layer plane direction and there are less than 2 Mg—Bi-based compounds having a diameter of 5.0 μm or more, and in the brazing material, there are less than 5 Bi particles having a diameter of 5.0 μm or more when observed in the surface layer plane direction.

Claims

1. An aluminum brazing sheet having a multilayer structure of two or more layers of at least a core material and a brazing material, wherein an Al—Si—Mg—Bi-based brazing material comprising, by mass %, 0.01% to 2.0% of Mg, 1.5% to 14.0% of Si, and 0.005% to 1.5% of Bi is clad on one surface or both surfaces of the core material at an outermost surface of the aluminum brazing sheet, in the Al—Si—Mg—Bi based brazing material, there are more than 10 Mg—Bi-based compounds having a diameter of 0.01 μm or more and less than 5.0 μm in terms of equivalent circle diameter per 10,000-μm.sup.2 visual field when observed in a surface layer plane direction and there are less than 2 Mg—Bi-based compounds having a diameter of 5.0 μm or more per 10,000-μm.sup.2 visual field, and in the brazing material, there are less than 5 Bi particles having a diameter of 5.0 μm or more in terms of equivalent circle diameter per 10,000-μm.sup.2 visual field when observed in the surface layer plane direction.

2. The aluminum brazing sheet according to claim 1, wherein in the Al—Si—Mg—Bi-based brazing material, a number of Si particles having a diameter of 1.75 μm or more in terms of equivalent circle diameter is 25% or more with respect to a number of Si particles having a diameter of 0.8 μm or more in terms of equivalent circle diameter when observed in the surface layer plane direction.

3. The aluminum brazing sheet according to claim 1, wherein in the Al—Si—Mg—Bi-based brazing material, an area ratio of Si particles having a diameter of 1.75 μm or more in terms of equivalent circle diameter with respect to a surface area is in a range of 0.1% to 1.5%.

4. The aluminum brazing sheet according to claim 1, wherein in the Al—Si—Mg—Bi-based brazing material, an atomic composition ratio between Mg and Bi is Mg/Bi=1.5 or more.

5. The aluminum brazing sheet according to claim 1, wherein in the Al—Si—Mg—Bi-based brazing material, a Ca content as impurities is in 100 ppm or less in terms of mass ppm.

6. The aluminum brazing sheet according to claim 1, wherein the Al—Si—Mg—Bi-based brazing material further comprises 0.1% to 9.0% of Zn by mass %.

7. The aluminum brazing sheet according to claim 1, wherein the core material comprises, by mass %, one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0%.

8. The aluminum brazing sheet according to claim 1, wherein the core material comprises, by mass %, Si: 0.05% to 1.2% and Mg: 0.01% to 2.0%, and further comprises one or two or more of Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0%.

9. The aluminum brazing sheet according to claim 1, wherein the core material is clad with a sacrificial material, and the sacrificial material comprises, by mass %, Zn: 0.1% to 9.0%, and further comprises one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, and Bi: 0.005% to 1.5%.

10. The aluminum brazing sheet according to claim 2, wherein in the Al—Si—Mg—Bi-based brazing material, an area ratio of Si particles having a diameter of 1.75 μm or more in terms of equivalent circle diameter with respect to a surface area is in a range of 0.1% to 1.5%.

11. The aluminum brazing sheet according to claim 2, wherein in the Al—Si—Mg—Bi-based brazing material, an atomic composition ratio between Mg and Bi is Mg/Bi=1.5 or more.

12. The aluminum brazing sheet according to claim 3, wherein in the Al—Si—Mg—Bi-based brazing material, an atomic composition ratio between Mg and Bi is Mg/Bi=1.5 or more.

13. The aluminum brazing sheet according to claim 10, wherein in the Al—Si—Mg—Bi-based brazing material, an atomic composition ratio between Mg and Bi is Mg/Bi=1.5 or more.

14. The aluminum brazing sheet according to claim 2, wherein the core material comprises, by mass %, one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0%.

15. The aluminum brazing sheet according to claim 3, wherein the core material comprises, by mass %, one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0%.

16. The aluminum brazing sheet according to claim 10, wherein the core material comprises, by mass %, one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0%.

17. The aluminum brazing sheet according to claim 2, wherein the core material comprises, by mass %, Si: 0.05% to 1.2% and Mg: 0.01% to 2.0%, and further comprises one or two or more of Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0%.

18. The aluminum brazing sheet according to claim 2, wherein the core material is clad with a sacrificial material, and the sacrificial material comprises, by mass %, Zn: 0.1% to 9.0%, and further comprises one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, and Bi: 0.005% to 1.5%.

19. The aluminum brazing sheet according to claim 3, wherein the core material is clad with a sacrificial material, and the sacrificial material comprises, by mass %, Zn: 0.1% to 9.0%, and further comprises one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, and Bi: 0.005% to 1.5%.

20. The aluminum brazing sheet according to claim 10, wherein the core material is clad with a sacrificial material, and the sacrificial material comprises, by mass %, Zn: 0.1% to 9.0%, and further comprises one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, and Bi: 0.005% to 1.5%.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0074] FIG. 1 is a view illustrating a brazing sheet for flux-free brazing according to an embodiment of the present invention.

[0075] FIG. 2 is a perspective view illustrating an aluminum heat exchanger for a vehicle according to the embodiment of the present invention.

[0076] FIG. 3 is a view illustrating a brazing evaluation model in an example of the present invention.

DESCRIPTION OF EMBODIMENTS

[0077] Hereinafter, an embodiment of the present invention will be described. An aluminum material used for a brazing sheet of the present invention can be manufactured, for example, by the following method. As an aluminum alloy for a brazing material, an Al—Si—Mg—Bi-based brazing material having a composition including, by mass %, 0.01% to 2.0% of Mg, 1.5% to 14.0% of Si, 0.005% to 1.5% of Bi, 0.1% to 9.0% of Zn by mass % as desired, and a remainder consisting of Al and inevitable impurities is prepared. The brazing material may contain, as other elements, 2.0% or less of In, Sn, and Mn, 1.0% or less of Fe, Ni, Ce, and Se, 0.3% or less of Be, Na, Sb, Ti, Zr, P, S, K, and Rb, and the like. Moreover, the brazing material is located at the outermost surface layer, and may have a brazing material with a different composition at the inner layer thereof. That is, the brazing material layer may have a plurality of layers. In a case of having the brazing material of the inner layer, the composition of the brazing material of the inner layer is not particularly limited, and examples thereof include an Al—Si-based brazing material and an Al—Si—Zn-based brazing material.

[0078] As an aluminum alloy for a core material, an aluminum alloy is adjusted to have a composition including, by mass %, one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%. Mn: 0.1% to 2.5%, Cu: 0.01% to 2.5%. Fe: 0.05% to 1.5%. Zr: 0.01% to 0.3%, Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%, Bi: 0.005% to 1.5%, and Zn: 0.1% to 9.0% and including a remainder consisting of Al and inevitable impurities.

[0079] In a case of using a sacrificial material, as an aluminum alloy for the sacrificial material, for example, an aluminum alloy is adjusted to have a composition including, by mass %, Zn: 0.1% to 9.0%, further including one or two or more of Si: 0.05% to 1.2%, Mg: 0.01% to 2.0%, Mn: 0.1% to 2.5%, Fe: 0.05% to 1.5%, Zr: 0.01% to 0.3%. Ti: 0.01% to 0.3%, Cr: 0.01% to 0.5%. Bi: 0.005% to 1.5%, and including a remainder consisting of Al and inevitable impurities.

[0080] An aluminum alloy is melted by preparing the composition of the present invention. The melting can be performed by a semi-continuous casting method. In the present invention, in order to disperse a fine Mg—Bi compound at the time before brazing, Mg and Bi are dissolved in an ingot as a solid solution to be supersaturated by performing rapid cooling from a high molten metal temperature during the casting of the brazing material. Specifically, the solid solubility of Mg and Bi can be increased by setting the molten metal temperature to 700° C. or higher. The obtained aluminum alloy ingot is subjected to a homogenization treatment under predetermined conditions. When the homogenization treatment temperature is low, a coarse Mg—Bi compound is precipitated and it is difficult to obtain the distributed state of the Mg—Bi compound of the present invention at the time before the brazing. Therefore, it is desirable to perform the treatment at a treatment temperature of 400° C. or higher for 1 to 10 hours.

[0081] Furthermore, in the present invention, in the number of Si particles contained in the brazing material and having an equivalent circle diameter of 0.8 μm or more, the number of Si particles having a diameter of 1.75 μm or more is desirably 25% or more. In order to obtain this material, the size and area ratio of the Si particles can be controlled by a solidification rate during the casting, the temperature and time of the homogenization treatment, a maximum reduction rate during hot rolling, and the like. For example, when the brazing material is cast, if the cooling rate is lower than 10° C./sec, the size of Si particles generated by solidification cooling becomes coarse. However, the Si particles are crushed in the subsequent rolling step, so that the above conditions can be satisfied. However, even in a case where this cooling rate becomes higher than 10° C./sec, when a heat treatment is performed, for example, under the condition of 500° C. or higher for several hours as the homogenization treatment after the casting, coarsening of the Si particles is achieved, and it is possible to obtain the Si particle size of the conditions of the present invention after the rolling as described above. Moreover, as for the reduction rate during the hot rolling, the larger the reduction rate of one rolling is, the finer the Si particles are crushed. By controlling these conditions in combination, the distribution of the Si particles (size, ratio of coarse particles, and area ratio) can be changed.

[0082] Next, the brazing material is assembled with the core material and the like and is subjected to hot clad rolling. At this time, in the present invention, the Mg—Bi compound is adjusted to a predetermined size and number density by controlling a rolling time at a predetermined temperature during the hot rolling, an equivalent strain from the start to the end of the hot rolling, a hot rolling finish temperature, and a cooling rate after the hot rolling.

[0083] First, by satisfying the rolling time in a predetermined temperature range during the hot rolling, precipitation of the Mg—Bi compound having a predetermined size defined in the present invention is promoted in an environment where dynamic strain is applied. Specifically, the precipitation of the fine Mg—Bi compound is promoted by setting the rolling time during which the material temperature during the hot rolling is between 400° C. and 500° C. to 10 minutes or more.

[0084] Furthermore, by controlling the equivalent strain from the start to the end of the hot rolling, a coarse Mg—Bi crystallized product generated during the casting can be crushed and refined. Specifically, the Mg—Bi crystallized product is sufficiently refined by adjusting a slab thickness and a finish thickness so that the equivalent strain E represented by Formula (1) satisfies ε>5.0.

ε=(2/√3)ln(t.sub.0/t)  Formula (1)

[0085] t.sub.0: Hot rolling start thickness (slab thickness)

[0086] t: Hot rolling finish thickness

[0087] Furthermore, when the hot rolling finish temperature is high and a state without dynamic strain is maintained, or when the cooling rate after the hot rolling is slow, a coarser Mg—Bi compound than desired by the present invention is precipitated at grain boundaries and the like. Therefore, by securing a cooling rate of a certain level or more by reducing the hot rolling finish temperature to a predetermined temperature, the precipitation of a coarse Mg—Bi compound is suppressed. Specifically, the precipitation of a coarse Mg—Bi compound is suppressed by setting the hot rolling finish temperature to 250° C. to 350° C. and controlling the cooling rate from the finish temperature to 200° C. to be faster than −20° C./hr. Thereafter, the brazing sheet of the present invention is obtained through cold rolling or the like. In the cold rolling, for example, cold rolling can be performed with a total reduction rate of 75% or more, process annealing can be performed at a temperature of 300° C. to 400° C., and then final rolling with a reduction rate of 40% can be performed. In cold rolling, the Mg—Bi compound is crushed and refined to some extent. However, since the size and number density thereof do not deviate from those targeted by the present invention, the conditions are not particularly limited. The process annealing may not be performed.

[0088] Furthermore, in the present invention, Bi particles contained in the Al—Si—Mg—Bi-based brazing material and having an equivalent circle diameter of 5.0 μm or more are desirably less than 5 in number per 10,000-μm.sup.2 visual field when observed in a surface layer plane direction before brazing. In order to obtain this material, adjustment can be achieved by appropriately combining the mixing ratio of Mg and Bi of the alloy, the molten metal temperature and the cooling rate during the casting, and the homogenization treatment conditions. For example, the generation of the Mg—Bi compound can be promoted by setting the mixing ratio of Mg and Bi blended in the brazing material to 1.5 or more in terms of atomic composition ratio. In the casting, the generation of the Mg—Bi compound can be promoted by reducing the cooling rate to less than 10° C./sec during the casting. Furthermore, in the homogenization treatment, the generation of the Mg—Bi compound in the ingot can be promoted by performing the homogenization treatment at a temperature as high 400° C. or higher.

[0089] Hot rolling and cold rolling are performed to obtain a clad material in which the brazing material is superimposed on and joined to one or both surfaces of the core material. Through the above process, as illustrated in FIG. 1, an aluminum brazing sheet 1 for a heat exchanger in which an aluminum alloy brazing material 3 is clad on one surface of an aluminum alloy core material 2 is obtained. In the figure, the brazing material is clad on one surface of the core material. However, the brazing material may be clad on both surfaces of the core material. Furthermore, a sacrificial material 10 or the like may be clad on the other surface of the core material. As a brazing target member 4, for example, by mass %, an aluminum alloy having a composition including Mg: 0.1% to 0.8%, Si: 0.1% to 1.2%, and a remainder consisting of Al and inevitable impurities is prepared and processed into a suitable shape. In the present invention, the composition of the brazing target member is not particularly limited.

[0090] In a case where a fin material for a heat exchanger is obtained by the cold rolling or the like, thereafter, corrugating or the like is performed as necessary. The corrugating process can be performed by passing between two rotating molds, enables satisfactory processing, and exhibits excellent formability.

[0091] The fin material obtained in the above process is subjected to brazing as an assembly combined with other constituent members (tube, header, and the like) as the constituent members of the heat exchanger. The assembly is disposed in a heating furnace having a non-oxidizing atmosphere under a normal pressure. A non-oxidizing gas can be constituted using an inert gas such as nitrogen gas, argon, a reducing gas such as hydrogen or ammonia, or a mixed gas thereof. Although the pressure of the atmosphere in a brazing furnace is basically the normal pressure, for example, in order to improve a gas replacement efficiency inside a product, a medium to low vacuum of about 100 kPa to 0.1 Pa in a temperature range before inciting the brazing material may be employed, or a positive pressure of 5 to 100 Pa from the atmospheric pressure may be employed in order to suppress the infiltration of outside air (atmosphere) into the furnace. These pressure ranges are included in a range of “without depressurization” in the present invention.

[0092] The heating furnace does not need to have a sealed space, and may be a tunnel type having a carry-in port and a carry-out port for the brazing material. Even in such a heating furnace, non-oxidizing properties are maintained by continuously blowing the inert gas into the furnace. The non-oxidizing atmosphere desirably has an oxygen concentration of 100 ppm or less by volume ratio.

[0093] In the above atmosphere, for example, heating is performed at a temperature rising rate of 10 to 200° C./min, and braze joining is performed under heat treatment conditions in which an attainment temperature of the assembly is 559° C. to 630° C. Under the brazing conditions, the brazing time is shortened as the temperature rising rate is increased, so that the growth of an oxide film on a material surface is suppressed and the brazability is improved. Brazing is possible when the attainment temperature is equal to or higher than at least the solidus temperature of the brazing material. However, the brazing material which flows increases in amount as the temperature approaches the liquidus temperature, and a good joined state is easily obtained at a joint having an open portion. However, when the temperature is too high, brazing erosion tends to proceed, and the structural dimensional accuracy of the assembly after brazing decreases, which is not preferable.

[0094] FIG. 2 illustrates an aluminum heat exchanger 5 in which fins 6 are formed using the aluminum brazing sheet 1 and a tube 7 made of an aluminum alloy is used as a brazing target material. The fin 6 and the tube 7 are assembled with a reinforcing member 8 and a header plate 9 to obtain the aluminum heat exchanger 5 for a vehicle or the like by flux-free brazing.

EXAMPLES

[0095] Various brazing sheets having the compositions shown in Tables 1 to 6 (core material, brazing material, sacrificial material; remainder consisting of Al and inevitable impurities) were produced into hot rolled sheets under the casting conditions and hot rolling conditions shown in Table 7. Specimens whose sacrificial material components are indicated by “-” do not use sacrificial materials. Thereafter, cold rolled sheets having a thickness of 0.30 mm and having an H14 equivalent grade were produced by cold rolling including process annealing. The clad ratio of each layer was 10% for the brazing material and 15% for the sacrificial material. Moreover, as the brazing target member, a corrugated fin of an aluminum bare material (0.06 mm thickness) of A3003 alloy and H14 was prepared.

[0096] A tube having a width of 25 mm was produced using the aluminum brazing sheet, and the tube and the corrugated fin were combined so that the tube brazing material and the corrugated fin are in contact with each other, thereby forming a core having a 15-stage tube and a length of 300 mm as a brazing evaluation model. The core was heated to 600° C. and held for 5 minutes in a brazing furnace in a nitrogen atmosphere (oxygen content 20 ppm), and the brazed state was evaluated. The evaluation results are shown in Tables 8 and 9.

Brazability

[0097] A joint ratio was obtained by the following formula, and superiority and inferiority between the samples were evaluated.

Fin joint ratio=(total brazing length of fin and tube/total contact length of fin and tube)×100

[0098] The determination was made according to the following criteria, and the results are shown in Tables 8 and 9.

[0099] Fin joint ratio after brazing A: 98% or more [0100] B: 90% or more and less than 98% [0101] C: 80% or more and less than 90% [0102] D: less than 80%

Joint Fillet Length

[0103] A portion of the brazed core was cut out, embedded in a resin, and mirror-polished, and the fillet length at a joint was measured using an optical microscope. As a measurement method, the width W of a joint 13 illustrated in FIG. 3 was measured at 20 points for each sample, and superiority or inferiority was evaluated by the average value thereof. The determination was based on the following criteria and shown in Tables 8 and 9.

[0104] A: 1.0 nm or more

[0105] B: 0.8 mm or more and less than 1.0 mm

[0106] C: 0.6 mm or more and less than 0.8 mm

[0107] D: less than 0.6 mm

Strength after Brazing

[0108] The brazing sheet was placed in a furnace in a drop form, and a brazing equivalent heat treatment was performed under the brazing conditions. Thereafter, the sample was cut out, a tensile test was conducted at room temperature by a normal method based on JIS, and a tensile strength was evaluated. The results are shown in Tables 8 and 9.

Corrosion Resistance

[0109] A brazing sheet having a sacrificial material was placed in a furnace in a drop form, and subjected to a brazing equivalent heat treatment under the brazing conditions. Thereafter, the sample was cut into a size of 30 mm×80 mm, masked except for the sacrificial material surface, and then subjected to Sea Water Acetic Acid Test (SWAAT, ASTM G85-A3) for 40 days. Corrosion products were removed from the sample after the corrosion test with chromic acid phosphate, and the corrosion depth was measured by observing the cross section of a maximum corrosion portion. The determination was based on the following criteria and shown in Tables 8 and 9.

[0110] A: In the sacrificial material layer

[0111] B: Within the half of the sheet thickness

[0112] C: Not penetrated

[0113] D: Penetrated

[0114] While all of the examples showed good brazability, the comparative examples did not obtain sufficient joining.

Ratio and Area Ratio of Si Particles Having Diameter of 1.75 μm or More on Surface of Brazing Material Layer

[0115] Regarding the produced aluminum clad material, the outermost surface of the brazing material was polished with 0.1-μm abrasive grains, and fully automatic particle analysis using an electron beam microanalyzer (EPMA) was performed on an observation visual field of 10,000 μm.sup.2 (corresponding to 100-μm square) for each sample from the surface direction. In the measurement, the ratio (%) of the number of Si particles having an equivalent circle diameter of 1.75 μm or more to the number of Si particles having an equivalent circle diameter of 0.8 μm or more was calculated, and furthermore, the area ratio (to the surface area) of the particles having an equivalent circle diameter of 1.75 μm or more was calculated. The measurement results are shown in Tables 1 and 2.

TABLE-US-00001 TABLE 1 Area Mg—Bi Mg—Bi Ratio of Si ratio of Si Atomic compound compound Bi particles particles composition Elements added to brazing material [wt %] Manufac- of less of 5 μm particles of 1.75 of 1.75 ratio Mg/Bi Ca turing than 5 μm or more [/10000 μm or μm or of brazing Specimen No. Mg Si Bi Zn (ppm) method [/10000 μm.sup.2] [/10000 μm.sup.2] μm.sup.2] more [%] more [%] material Example 1 0.01 7.5 0.3 — 8 E 14 1 4 35 0.4 0.3 2 0.1 7.5 0.3 — 8 D 36 0 3 44 0.5 2.9 3 1.5 7.5 0.3 — 8 46 0 2 35 0.5 43.0 4 2.0 7.5 0.3 — 8 47 0 2 33 0.6 57.3 5 0.5 1.5 0.3 — 8 F 54 0 35 0.1 14.3 6 0.5 3.0 0.3 1.0 8 A 45 0 3 35 0.2 14.3 7 0.5 12.0 0.3 2.0 8 56 0 2 38 1.1 14.3 8 0.5 14.0 0.3 — 8 B 39 0 35 1.5 14.3 9 0.5 7.5 0.005 — 8 J 18 0 1 39 0.5 859.8 10 0.5 7.5 0.05 — 8 I 28 0 2 40 0.5 8 .0 11 0.5 7.5 0.5 — 8 C 62 0 3 35 0.6 8.6 12 0.5 7.5 1.5 — 8 B 67 0 4 35 0.6 2.9 13 0.5 7.5 0.3 0.1 8 A 44 0 35 0.5 14.3 14 0.5 7.5 0.3 0.5 8 D 46 0 3 44 0.5 14.3 15 0.5 7.5 0. 7.0 8 G 53 0 3 35 0.5 14.3 16 0.5 7.5 0.3 9.0 8 B 34 0 35 0.5 14.3 17 0.5 7.5 0.3 — 90 I 56 0 2 40 0.5 14.3 18 0.5 7.5 0. 3.0 8 H 44 0 3 35 0.5 14.3 19 0.5 7.5 0.3 3.0 50 C 38 0 3 37 0.5 14.3 20 0.5 7.5 0.3 — 8 J 58 0 2 40 0.5 14.3 21 0.5 7.5 0. 1.0 8 F 50 0 3 35 0.5 14.3 22 0.05 10.5 0.5 1.0 8 E 31 0 3 34 0.6 0.9 23 0.3 10.5 0.7 3.0 8 B 54 0 3 35 0.7 3.7 24 0.3 10.5 0.7 3.0 8 C 57 0 3 40 0.7 3.7 25 0.7 10.5 0.2 — 8 H 43 0 3 35 0.8 30.1 26 0.7 10.5 0.2 — 120 D 45 0 2 43 0.8 30.1 27 0.2 10.5 0.2 — 8 A 25 0 3 35 0.6 8.6 28 0.7 10.5 0.2 — 8 B 34 0 2 35 0.8 30.1 29 0.7 10.5 0.2 — 8 D 44 0 3 44 0.8 30.1 30 0.2 10.5 0.2 — 8 A 26 0 3 35 0.6 8.6 31 0.01 7.5 0.3 — 8 E 14 1 4 35 0.4 0.3 32 0.1 7.5 0.3 — 8 D 26 0 44 0.5 2. 33 1.5 7.5 0.3 — 8 B 46 0 2 35 0.5 43.0 34 2.0 7.5 0.3 — 8 H 47 0 2 33 0.6 57.3 35 0.5 1.5 0.3 — 8 F 54 0 35 0.1 14.3 36 0.5 3.0 0.3 1.0 8 A 45 0 3 35 0.2 14.3 37 0.5 12.0 0.3 2.0 8 56 0 2 38 1.1 14.3 38 0.5 14.0 0.3 — 8 B 39 0 3 35 1.5 14.3 39 0.5 .5 0.005 — 8 J 18 0 39 0.5 859.8 40 0.5 7.5 0.05 — 8 28 0 2 40 0.5 86.0 41 0.5 7.5 0.5 — 8 C 62 0 3 35 0.6 8.6 42 0.5 7.5 1.5 — 8 B 67 0 4 35 0.6 2. 43 0.5 7.5 0.3 0.1 8 A 44 0 3 35 0.5 14.3 44 0.5 7.5 0.3 0.5 8 D 46 0 44 0.5 14.3 45 0.5 7.5 0.3 7.0 8 53 0 3 35 0.5 14.3 46 0.5 7.5 0.3 9.0 8 B 34 0 3 35 0.5 14.3 47 0.5 7.5 0.3 — 90 I 56 0 2 40 0.5 14.3 48 0.5 7.5 0.3 3.0 8 H 44 0 3 35 0.5 14.3 49 0.5 7.5 0.3 3.0 50 C 38 0 3 37 0.5 14.3 50 0.5 7.5 0.3 — 8 58 0 2 40 0.5 14.3 51 0.5 7.5 0.3 1.0 8 50 0 3 35 0.5 14.3 52 0.05 10.5 0.5 1.0 8 E 31 0 3 34 0.6 0.9 53 0.3 10.5 0.7 3.0 8 B 54 0 3 35 0.7 .7 54 0.3 10.5 0.7 3.0 8 C 57 0 3 40 0.7 3.7 55 0.7 10.5 0.2 — 8 H 43 0 3 35 0.8 30.1 56 0.7 10.5 0. — 120 D 45 0 2 43 0.8 30.1 57 0.2 10.5 0.2 — 8 A 25 0 3 35 0.6 8.6 58 0.7 10.5 0.2 — 8 B 34 0 3 35 0.8 30.1 59 0.7 10.5 0. — 8 D 44 0 3 44 0.8 30.1 60 0.2 10.5 0.2 — 8 A 26 0 3 35 0.6 8.6 81 0.5 1.5 0.3 — 8 50 0 2 28 0.08 14.3 82 0.5 1.5 0.3 — 8 Q 48 0 2 23 0.07 14.3 83 1.5 7.5 0.3 — 8 40 0 2 25 0.3 43.0 84 0.09 10.5 0.5 1   8 E 38 0 3 34 0.6 1.5 85 0.5 7.5 0.3 — 100 56 0 2 40 0.5 14.3 indicates data missing or illegible when filed

TABLE-US-00002 TABLE 2 Area Mg—Bi Mg—Bi Ratio of Si ratio of Si Atomic compound compound Bi particles particles concentration Elements added to brazing material [wt %] Manufac- of less of 5 μm particles of 1.75 of 1.75 ratio Mg/Bi Ca turing than 5 μm or more [/10000 μm or μm or of brazing Specimen No. Mg Si Bi Zn (ppm) method [/10000 μm.sup.2] [/10000 μm.sup.2] μm.sup.2] more [%] more [%] material Compar- 61 0.005 7.5 0.3 — 8 B 9 3 3 35 0.3 0.1 ative 62 2.2 7.5 0.3 — 8 Cannot be evaluated due to improper production 63.1 Example 63 0.5 1.4 0.3 1.0 8 51 0 3 35 0.05 14.3 64 0.5 15.0 0.3 1.0 8 Cannot be evaluated due to improper production 14.3 65 0.5 7.5 0.003 — 8 C 7 6 2 35 0.4 1433.0 66 0.5 7.5 1.6 — 8 Cannot be evaluated due to improper production 2.7 67 0.3 7.5 0.1 — 8 M 8 5 2 25 0.7 25.8 68 0.5 7.5 0.1 — 8 L 7 6 5 22 0.8 43.0 69 0.2 10.5 0.1 2.0 8 K 9 3 2 26 0.6 17.2 70 0.5 10.5 0.3 2.0 8 O 8 5 3 20 0.9 14.3 71 0.2 10.5 0.005 — 50 N 9 5 4 18 1.0 343.9 72 0.5 10.5 0.3 3.0 8 L 9 5 6 21 0.8 14.3 Reference 73 0.5 10.5 0.5 1.0 8 C 36 0 3 35 0.6 8.6 Example 74 0.5 10.5 0.2 1.0 8 Cannot be evaluated due to improper production 21.5 75 0.7 10.5 0.2 — 8 Cannot be evaluated due to improper production 30.1 76 0.7 10.5 0.2 — 8 Cannot be evaluated due to improper production 30.1 77 0.7 7.5 0.3 — 8 Cannot be evaluated due to improper production 20.1 78 0.7 7.5 0.3 — 8 Cannot be evaluated due to improper production 20.1 79 0.5 7.5 0.3 — 8 Cannot be evaluated due to improper production 14.3 80 0.5 7.5 0.1 — 8 A 28 0 3 33 0.4 43.0 indicates data missing or illegible when filed

TABLE-US-00003 TABLE 3 Core material composition [wt %] Specimen No. Si Mg Mn Cu Fe Zr Ti Cr Bi Zn Example 1 0.6 0.5 — — — — — — — — 2 0.6 0.5 — — — — — — — — 3 0.6 0.5 0.5 — 0.3 — — — 0.005 — 4 0.6 0.5 0.5 — 0.3 — — — 0.01 — 5 0.6 0.5 0.5 — 0.3 — — — 0.01 — 6 0.6 0.5 0.5  0.02 — — 0.02 — 7 0.6 0.5 0.3  0.05 — — — 0.02 — — 8 0.6 0.5 0.1 — — — — 0.2 — — 9 0.6 0.5 1.5 — — 0.1 — 0.2 — — 10 0.6 0.5 1.0 — — 0.1 — — — — 11 0.6 0.5 0.5 0.5 — 0.1 — — — — 12 0.6 0.5 0.5 0.5 — 0.1 — — 0.05 — 13 0.6 0.5 0.5 0.3 — — — — 0.05 — 14 0.6 0.5 0.5 0.3 0.3 — — — 0.3 — 15 0.6 0.5 0.5 1.0  0.05 — — — 0.3 — 16 0.6 0.5 0.5 1.0 0.3 — — — 0.5 — 17 0.6 0.5 0.5 — 0.3 — — — 0.5 — 18 0.05 0.5 0.5 — 0.3 — — — — — 19 0.1 0.5 0.5 — 0.3 — — — — — 20 1.0 0.5 0.5 — 0.3 — — — — — 21 1.2 0.5 0.5 — 0.3 — — — — 0.5 22 0.6 0.01 0.5 0.2 0.5 — — — — 0.5 23 0.6 0.05 0.5 0.2 0.5 — — — — 0.3 24 0.6 1.0 0.5 0.2 — — — — — 0.2 25 0.6 2.0 0.5 — — — 0.1 — — — 26 0.6 0.5 0.5 — — — 0.1 — — — 27 0.6 0.5 0.5 — — — 0.1 — — — 28 0.6 0.5 0.5 — — — 0.1 29 0.6 1.0 0.5 — 0.3 — — — — — 30 0.6 1.0 0.5 — 0.3 — — — — — 31 0.6 0.5 — — — — — — — — 32 0.6 0.5 — — — — — — — — 33 0.6 0.5 0.5 — 0.3 — — — 0.005 — 34 0.6 0.5 0.5 — 0.3 — — — 0.01 — 35 0.6 0.5 0.5 — 0.3 — — — 0.01 — 36 0.6 0.5 0.5  0.02 0.2 — — 0.02 — 37 0.6 0.5 0.3  0.05 — — — 0.02 — — 38 0.6 0.5 0.1 — — — — 0.2 — — 39 0.6 0.5 1.5 — — 0.1 — 0.2 — — 40 0.6 0.5 1.0 — — 0.1 — — — — 41 0.6 0.5 0.5 0.5 — 0.1 — — — — 42 0.6 0.5 0.5 0.5 — 0.1 — — 0.05 — 43 0.6 0.5 0.5 0.3 — — — — 0.05 — 44 0.6 0.5 0.5 0.3 0.3 — — — 0.3 — 45 0.6 0.5 0.5 1.0  0.05 — — — 0.3 — 46 0.6 0.5 0.5 1.0 0.3 — — — 0.5 — 47 0. 0.5 0.5 — 0.3 — — — 0.5 — 48 0.05 0.5 0.5 — 0.3 — — — — — 49 0.1 0.5 0.5 — 0.3 — — — — — 50 1.0 0.5 0.5 — 0.3 — — — — — 51 1.2 0.5 0.5 — 0.3 — — — — 0.5 52 0.6 0.01 0.5 0.2 0.5 — — — — 0.5 53 0.6 0.05 0.5 0.2 0.5 — — — — 0.3 54 0.6 1.0 0.5 0.2 — — — — — 0.2 55 0.6 2.0 0.5 — — — 0.1 — — — 56 0.6 0.5 0.5 — — — 0.1 — — — 57 0.6 0.5 0.5 — — — 0.1 — — — 58 0.6 0.5 0.5 — — — 0.1 59 0.6 1.0 0.5 — 0.3 — — — — — 60 0.6 1.0 0.5 — 0.3 — — — — — 81 0.6 0.5 0.5 — 0.3 — — — 0.01 — 82 0.6 0.5 0.5 — 0.3 — — — 0.01 — 83 0.6 0.5 0.5 — 0.3 — — — 0.005 — 84 0.6 0.0 0.5 0.5 — — — — 0.5 85 0.6 0.5 0.5 — 0.3 — — — 0.5 — indicates data missing or illegible when filed

TABLE-US-00004 TABLE 4 Core material composition [wt %] Specimen No. Si Mg Mn Cu Fe Zr Ti Cr Bi Zn Compar- 61 0.6 0.5 — — — — — — — — ative 62 0.6 0.5 — — — — — — — — Example 63 0.6 0.5 0.5 — 0.3 — — —  0.01 — 64 0.6 0.5 0.5  0.02 0.2 — — 0.02 — 65 0.6 0.5 1.5 — — 0.1 — 0.2  — — 66 0.6 0.5 1.0 — — 0.1 — — — — 67 0.6 0.5 0.5 0.3 — — — —  0.05 — 68 0.6 0.5 0.5 0.3 0.3 — — — 0.3 — 69 0.6 0.5 0.5 1.0  0.05 — — — 0.3 — 70 0.6 0.5 0.5 1.0 0.3 — — — 0.5 — 71 0.6 0.5 0.5 — 0.3 — — — 0.5 — 72 0.05 0.5 0.5 — 0.3 — — — — — Reference 73 1.5 0.5 0.2 1.0 0.2 — — — — — Example 74 0.5 2.1 0.5 0.5 0.2 — — — — — 75 0.5 0.5 2.6 0.5 0.2 — — — — — 76 0.5 0.5 0.1 2.6 0.2 — — — — — 77 0.5 0.5 1.5 0.5 1.6 — — — — — 78 0.8 0.5 — 0.5 0.2  0.31 0.32 — — — 79 0.5 0.5 — 0.5 0.2 — 0.21 0.51 — — 80 1.1 0.5 — 1.2 0.2 — — — — 9.1

TABLE-US-00005 TABLE 5 Sacrificial material composition [wt %] Specimen No. Zn Si Mg Mn Fe Zr Ti Cr Bi Example 1 — — — — — — — — — 2 — — — — — — — — — 3 — — — — — — — — — 4 — — — — — — — — — 5 — — — — — — — — — 6 — — — — — — — — — 7 — — — — — — — — — 8 — — — — — — — — — 9 — — — — — — — — — 10 — — — — — — — — — 11 — — — — — — — — — 12 — — — — — — — — — 13 — — — — — — — — — 14 — — — — — — — — — 15 — — — — — — — — — 16 — — — — — — — — — 17 — — — — — — — — — 18 — — — — — — — — — 19 — — — — — — — — — 20 — — — — — — — — — 21 — — — — — — — — — 22 — — — — — — — — — 23 — — — — — — — — — 24 — — — — — — — — — 25 — — — — — — — — — 26 — — — — — — — — — 27 — — — — — — — — — 28 — — — — — — — — — 29 — — — — — — — — — 30 — — — — — — — — — 31 3.0 — — — — — — — — 32 3.0 — — — — — — — — 33 3.0 0.5 — 0.5 — — — — — 34 3.0 0.5 — 0.5 — — — — — 35 1.0 0.5 — 0.5 — — — — — 36 8.0 0.5 — 0.5 — — — — — 37 3.0 0.5 — 0.4 — 0.1 — — — 38 3.0 0.5 — 0.4 — 0.1 — — — 39 3.0 0.5 — 1.0 — 0.1 — — — 40 3.0 0.5 0.3 1.0 — 0.1 — — — 41 3.0 — 0.3 — — — 0.1 — — 42 3.0 — 0.3 — — — 0.1 — — 43 3.0 — 0.3 — — — 0.1 — — 44 3.0 — 1.0 — 0.2 — 0.1 — — 45 3.0 — 1.0 — 0.2 — — 0.1 — 46 3.0 — 1.0 — 0.2 — — 0.1 — 47 3.0 — 1.0 — 0.2 — — 0.1 0.05 48 3.0 — — — 0.5 — — 0.1 0.05 49 3.0 — — — 0.5 — — — 0.05 50 3.0 — — — 0.5 — — — 0.05 51 3.0 — — 0.5 — — — — 0.5 52 3.0 — — 0.5 — — — — 0.5 53 3.0 — — 0.5 — — — — 0.5 54 3.0 0.5 — 1.5 — — — — — 55 3.0 0.5 — 1.5 — — — — — 56 3.0 0.5 — 0.5 — — — — — 57 3.0 0.5 — 0.5 — — — — 0.3 58 3.0 0.5 — 0.5 — — — — 0.3 59 3.0 0.5 — 0.5 — — — — 0.3 60 3.0 0.5 — 0.5 — — — — 0.3 81 — — — — — — — — — 82 — — — — — — — — — 83 — — — — — — — — — 84 — — — — — — — — — 85 — — — — — — — — —

TABLE-US-00006 TABLE 6 Sacrificial material composition [wt %] Specimen No. Zn Si Mg Mn Fe Zr Ti Cr Bi Compar- 61 — — — — — — — — — ative 62 — — — — — — — — — Example 63 — — — — — — — — — 64 — — — — — — — — — 65 — — — — — — — — — 66 — — — — — — — — — 67 — — — — — — — — — 68 — — — — — — — — — 69 — — — — — — — — — 70 — — — — — — — — — 71 — — — — — — — — — 72 — — — — — — — — — Reference 73 — — — — — — — — — Example 74 — — — — — — — — — 75 — — — — — — — — — 76 — — — — — — — — — 77 — — — — — — — — — 78 — — — — — — — — — 79 — — — — — — — — — 80 — — — — — — — — —

TABLE-US-00007 TABLE 7 Brazing material Casting Homogenization Hot rolling conditions condition condition Rolling time Molten metal Temperature between 400° C. Equivalent Finish Cooling temperature and time and 500° C. strain temperature rate Specimen No. (° C.) (° C., h) (min) (° C.) (° C./h) Target A 710 450° C., 5 h 15 5.7 320 25 range B 715 450° C., 5 h 14 5.4 334 21 C 715 500° C., 2 h 10 5.5 355 35 D 725 550° C., 2 h 14 5.5 274 28 E 725 400° C., 8 h 18 5.9 290 38 F 735 400° C., 8 h 22 5.7 252 35 G 735 450° C., 8 h 15 6.1 315 42 H 720 450° C., 8 h 24 5 340 34 I 755 500° C., 5 h 14 6.4 347 52 J 745 500° C., 5 h 30 5 290 32 P 700 400° C., 8 h 22 5.7 260 40 Q 690 400° C., 8 h 21 5.7 270 42 R 700 420° C., 5 h 14 5.2 334 18 Outside K 695 400° C., 8 h 15 5.3 267 18 the L 680 380° C., 8 h 8 5.2 220 12 target M 715 380° C., 8 h 22 4.8 337 36 N 670 350° C., 8 h 15 4.6 395 22 O 705 350° C., 8 h 7 5.7 322 35 indicates data missing or illegible when filed

TABLE-US-00008 TABLE 8 Strength Brazability after Joint Fillet brazing Corrosion Specimen No. ratio length [MPa] resistance Example 1 C C 136 — 2 B B 136 — 3 C B 157 — 4 C C 159 — 5 B C 152 — 6 B C 152 — 7 A A 148 — 8 A B 143 — 9 A B 166 — 10 A A 159 — 11 A A 165 — 12 A B 165 — 13 A A 158 — 14 A A 163 — 15 A A 187 — 16 A A 189 — 17 A B 151 — 18 A A 128 — 19 A B 130 — 20 A A 164 — 21 B B 172 — 22 C C 134 — 23 B C 137 — 24 A B 182 — 25 A C 221 — 26 A C 151 — 27 A A 148 — 28 A A 151 — 29 A B 175 — 30 A B 173 — 31 C C 143 A 32 B B 143 A 33 C B 164 A 34 C C 160 A 35 B C 159 B 36 B C 159 B 37 A A 155 A 38 A B 150 A 39 A B 173 A 40 A A 160 A 41 A A 172 A 42 A B 172 A 43 A A 165 A 44 A A 170 A 45 A A 194 A 46 A A 196 A 47 A B 158 A 48 A A 135 A 49 A B 137 A 50 A A 171 A 51 B B 179 A 52 C C 141 A 53 B C 144 A 54 A B 189 A 55 A C 228 A 56 A C 158 A 57 A A 155 A 58 A A 158 A 59 A B 182 A 60 A B 180 A 81 C C 152 — 82 C C 152 — 83 C C 157 — 84 B B 134 — 85 A C 151 —

TABLE-US-00009 TABLE 9 Strength Brazability after Specimen Joint Fillet brazing Corrosion No. ratio length [MPa] resistance Comparative 61 D D 143 — Example 62 Cannot be evaluated due — to improper production 63 C D 159 — 64 Cannot be evaluated due — to improper production 65 D D 173 — 66 Cannot be evaluated due — to improper production 67 C D 164 — 68 D D 170 — 69 C D 193 — 70 D D 196 — 71 D D 157 — 72 D D 135 — Reference 73 Core material melted during brazing — Example 74 Cannot be evaluated due — to improper production 75 Cannot be evaluated due — to improper production 76 Cannot be evaluated due — to improper production 77 Cannot be evaluated due — to improper production 78 Cannot be evaluated due — to improper production 79 Cannot be evaluated due — to improper production 80 Core material melted during brazing —

REFERENCE TO DEPOSITED BIOLOGICAL MATERIAL

[0116] 1 aluminum brazing sheet [0117] 2 aluminum alloy core material (aluminum alloy core material layer) [0118] 3 aluminum alloy brazing material (aluminum alloy brazing material layer) [0119] 4 target member [0120] 5 aluminum heat exchanger [0121] 6 fin [0122] 7 tube [0123] 10 sacrificial material (sacrificial material layer) [0124] 13 joint [0125] 15 tube