JP2000297339A - Aluminum alloy clad material for heat exchanger, excellent in corrosion resistance under alkaline environment and acid environment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aluminum alloy clad material for heat exchanger, excellent in corrosion resistance. SOLUTION: This aluminum alloy clad material consists of a core material, an Al-Si or Al-Si-Zn brazing filler metal, and a sacrificial anode cladding material. At this time, the core material is composed of an Al alloy which has a composition consisting of 0.8-1.8% Mn, 0.1-1.0% Cu, and the balance Al with inevitable impurities and containing, if necessary, 0.4-1.5% Fe or 0.4-1.5% Fe and 0.1-1.0%; Si and further containing, if necessary, either or both of 0.05-O.2% Ti and 0.05-O.2% Zr, and the cladding material has a composition consisting of 0.02-1.5% Mn and the balance Al with inevitable impurities and containing, if necessary, either or both of 0.3-2.0% Fe and 0.1-1.0% Ni and further containing, if necessary, one or two kinds among 0.1-0.8% Si, 0.005-0.2% In, and 0.05-0.2% Sn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum alloy clad material used as a structural member such as a heat exchanger having excellent corrosion resistance in a wide pH range from an alkaline environment to an acidic environment. Aluminum alloy clad material is a material that can be applied as a coolant flow path structural member of aluminum heat exchangers such as radiators and heater cores for automobiles manufactured by inert gas atmosphere brazing and vacuum brazing using flux, for example, tube material It is.

[0002]

2. Description of the Related Art Conventionally, as a tube material for a radiator or a heater core of an automobile, an Al-Si-based brazing material or Al-Si-
A three-layer aluminum alloy clad material in which a Zn-based brazing material is clad and an Al-Zn-based alloy is clad on the other surface of the core material as a sacrificial anode skin material is used. The most commonly used aluminum alloy clad material is JIS 3003 (% by weight, Mn: 1.0-1.
5%, Cu: 0.1 to 0.2%, Si: 0.6% or less,
Fe: 0.75% or less, balance: Al-Mn-based alloy composed of Al and unavoidable impurities) as a core material, and one surface of the core material is clad with an Al-Zn-based alloy sacrificial anode skin material of JIS 7072, An aluminum alloy clad material in which an Al-Si-based or Al-Si-Zn-based brazing material is clad on the other surface of the core material is known.

[0003] The aluminum alloy clad material Al-
The Si-based or Al-Si-Zn-based brazing material is used for joining a tube material and a fin material and joining a tube material to a header plate during brazing, and the sacrificial anode skin material has electrochemical properties with the core material. In this case, the skin material is mainly corroded due to the difference between them, and the function of suppressing the progress of corrosion in the core material is achieved. When these aluminum alloy clad materials are used in a heat exchanger as a tube material of a radiator or a heater core, they exhibit an excellent sacrificial anode effect in a weakly acidic to neutral region. Therefore, LL consisting of antifreeze and rust inhibitor
The cooling water of the heat exchanger to which C (long life coolant) is added at about 5 to 50% is controlled to be neutral to weakly alkaline (pH 8 or less). However, the cooling water to which LLC (long life coolant) is actually used is often poor in quality of LLC or shows strong alkalinity of pH 9 or more due to dissolution of metal ions. In a heat exchanger containing cooling water that has become alkaline, pitting occurs early and its life is shortened.

[0004] In order to improve these, in terms of% by weight (% indicates% by weight) (a) Mn: 1.0 to 1.5%, Fe: 0.7% or less,
Si: 0.6% or less, Cu: 0.05-0.2%, Z
n: an Al-Si-based or Al-Si-Zn-based brazing material is clad on one surface of a core material containing 0.1% or less, the balance being an Al alloy having a composition of Al and inevitable impurities, On the other surface of the core material, Zn: 0.1 to
Aluminum alloy cladding for heat exchangers with excellent corrosion resistance, clad with a sacrificial anode skin material having a composition of 1.5%, Fe: more than 0.7 to 1.2%, and the balance consisting of Al and unavoidable impurities (See JP-A-10-17967), (b) Mn: 0.3 to 2.0% and Cu:
0.10 to 0.8% of one or two kinds, if necessary, Mg: 0.1 to 0.5%, Si: 0.1 to 1%, and if necessary, Cr: 0.05-0.3
%, Zr: 0.05-0.3%, Ti: 0.05-0.
3%, B: one or two or more of B: 0.01 to 0.1%, and the other one side of a core material made of an Al alloy having a composition consisting of Al and unavoidable impurities has Al- Si
Or Al-Si-Zn brazing material is clad, and on the other surface of the core material, Zn: 1.5-4.0%, Fe:
Contains more than 0.5% and not more than 3%, and optionally Mg:
0.1-2.5%, Sn: 0.01-0.2%, Ga:
One or more of 0.01 to 0.2%, Cr: 0.05 to 0.3%, Zr: 0.05
~ 0.3%, Ti: 0.05 ~ 0.3%, B: 0.01
-0.1, Mn: 0.1-2.0%, Si: 0.1-1
% Of an aluminum alloy clad material for heat exchangers, which is excellent in corrosion resistance and is clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. Reference), and the like.

[0005]

A good corrosion resistance is obtained by flowing cooling water in a wide pH range from a weakly acidic solution to an alkaline solution through a tube of a radiator or a heater core made of the conventional improved aluminum alloy clad material. However, its corrosion resistance is not yet sufficient, and there is a need for an aluminum alloy clad material having further excellent corrosion resistance. In particular, in recent years, heat exchangers for automobiles have been required to have higher performance, lighter weight, and lower cost, and as a result, tubes have become thinner year by year. However, thinner tubes require more corrosion resistance than before,
If LLC (Long Life Coolant) added to the cooling water is inferior and shows strong alkalinity of pH 9 or more, the radiator or heater core tube made of the above-mentioned conventional improved aluminum alloy clad material for a heat exchanger may be used as an early stage. There was a problem that a sufficient life was not obtained due to the formation of through holes.

[0006]

In view of the above, the present inventors have sought to obtain not only sufficient corrosion resistance when circulating a weakly acidic and neutral cooling water but also a strong alkaline cooling water having a pH of 9 or more. As a result of conducting research to obtain an aluminum alloy clad material with sufficient corrosion resistance even if
(A) A conventional aluminum alloy clad material for a heat exchanger contains a large amount of Zn in a sacrificial anode skin material.
When strong alkaline cooling water with a pH of 9 or more is circulated through a radiator or a heater core tube made of an aluminum alloy clad material clad with a sacrificial anode skin material containing Zn, the film formed on the sacrificial anode skin material containing Zn is a brittle film In particular, when the strong alkaline cooling water having a pH of 9 or more is circulated at a high speed, the coating is peeled off at an early stage, and the sacrificial anode skin material is quickly consumed, thereby shortening the life of the tube. , (B)
Prevents the formation of a brittle and easily peelable film without adding Zn as a sacrificial anode skin material, and furthermore protects the hydroxide film formed by adding Mn alone or one or two of Mn, Fe and Ni. In contrast, the potential difference between the sacrificial anode skin material and the core material is ensured by adding Cu to the core material to make the core material more noble. A radiator or heater core tube made of an aluminum alloy clad material clad with a sacrificial anode skin material added with Ni and a core material added with Cu has improved corrosion resistance particularly against strongly alkaline cooling water having a pH of 9 or more. (C) the above-mentioned Cu
The specific configuration of an aluminum alloy clad material in which a sacrificial anode skin material having a composition not containing Zn is clad on a core material having a composition containing (i) Mn: 0.8 to 1.8%, Cu: 0.
A core material composed of an Al alloy containing 1 to 1.0% and the balance of Al and unavoidable impurities, (ii) Mn:
0.8 to 1.8%, Cu: 0.1 to 1.0%,
Further, a core material comprising an Al alloy containing 0.4 to 1.5% of Fe and the balance of Al and inevitable impurities, (iii) Mn: 0.8 to 1.8%, Cu: 0. 1 to
1.0%, Fe: 0.4-1.5%, S
i: a core material composed of an Al alloy containing 0.1 to 1.0%, with the balance being Al and inevitable impurities, (iv)
The core material of (i) to (iii) further contains Ti: 0.05 to
0.2%, Zr: a core material containing an Al alloy containing one or two of 0.05 to 0.2%, with the balance being Al and unavoidable impurities; (Iv)
An Al-Si-based or Al-Si-Zn-based brazing material is clad on one surface of one of the core materials, and the other of the core materials in any one of the above (i) to (iv). On one side,
(I) Mn: 0.02 to 1.5%, the remainder being Al
And a sacrificial anode skin material made of an Al alloy having a composition of unavoidable impurities, (II) containing 0.02 to 1.5% of Mn, further containing 0.3 to 2.0% of Fe, and 0.1 of Ni. ~
A sacrificial anode skin material composed of an Al alloy having a composition comprising 1.0% or 1.0% and the balance being Al and unavoidable impurities, (III) Mn: 0.02 to 1.5% And Fe: 0.3-2.0%, Ni: 0.1-
1.0% of one or two kinds, further containing Si:
A sacrificial anode skin material comprising an Al alloy having a composition of 0.1 to 0.8%, with the balance being Al and unavoidable impurities,
(IV) Mn: 0.02 to 1.5%, and F
e: 0.3 to 2.0%, Ni: 0.1 to 1.0%, one or two of which are contained, and In: 0.005 to
0.5%, Sn: any one of a sacrificial anode skin material containing one or two of 0.005 to 0.5% and the balance being an Al alloy having a composition of Al and unavoidable impurities. It is preferable to clad the sacrificial anode skin material,
The research result was obtained.

[0007] The present invention has been made based on the results of the research, and (1) Mn: 0.8 to 1.8%,
Cu: Al-Si-based or Al-Si-Zn-based brazing material is coated on one surface of a core material containing 0.1 to 1.0%, the balance being an Al alloy having a composition of Al and unavoidable impurities. Clad, and Mn: 0.
An aluminum alloy clad material for a heat exchanger, which is excellent in corrosion resistance and is clad with a sacrificial anode skin material having a composition containing 02 to 1.5% and a balance of Al and inevitable impurities,
(2) Mn: 0.8-1.8%, Cu: 0.1-1.0
%, Fe: 0.4 to 1.5%, the balance being made of an Al-Si or Al-Si-Zn on one surface of a core material made of an Al alloy having a composition of Al and inevitable impurities.
A brazing material is clad, and on the other side of the core material, Mn:
An aluminum alloy clad material for heat exchangers having excellent corrosion resistance obtained by cladding a sacrificial anode skin material having a composition of 0.02 to 1.5% and the balance of Al and unavoidable impurities, (3) Mn: 0.1 to 0.1%. 8 to 1.8%, Cu: 0.1 to
1.0%, Fe: 0.4 to 1.5%, Si: 0.1 to
One side of a core material made of an Al alloy having a composition of 1.0% and the balance of Al and unavoidable impurities is provided on one surface of the core material.
-Si or Al-Si-Zn brazing material is clad, and Mn: 0.02 to 1.5%
, A clad aluminum alloy clad material for heat exchangers having excellent corrosion resistance and clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities.
8 to 1.8%, Cu: 0.1 to 1.0%, Ti: 0.05 to 0.2%, Zr: 0.05 to 0.2
% Of a core material containing an Al alloy having a composition containing Al and unavoidable impurities, and clad with an Al-Si-based or Al-Si-Zn-based brazing material on one surface of the core material. Then, on the other side of the core material, Mn: 0.
An aluminum alloy clad material for a heat exchanger, which is excellent in corrosion resistance and is clad with a sacrificial anode skin material having a composition containing 02 to 1.5% and a balance of Al and inevitable impurities,
(5) Mn: 0.8-1.8%, Cu: 0.1-1.0
%, Fe: 0.4 to 1.5%, and further Ti:
0.05 to 0.2%, Zr: one or two of 0.05 to 0.2% of the core material, and the balance is one of core materials made of an Al alloy having a composition of Al and unavoidable impurities. An Al-Si or Al-Si-Zn brazing material is clad on one surface, and Mn: 0.02 to
An aluminum alloy clad material for heat exchangers having excellent corrosion resistance, which is formed by cladding a sacrificial anode skin material having a composition of 1.5% and the balance of Al and inevitable impurities, (6) M
n: 0.8 to 1.8%, Cu: 0.1 to 1.0%, F
e: 0.4 to 1.5%, Si: 0.1 to 1.0%, Ti: 0.05 to 0.2%, Zr: 0.05
０．２0.2%, one or two of which are Al
And an Al-Si-based or Al-Si-
A Zn-based brazing material is clad, and on the other side of the core material, M
n: an aluminum alloy clad material for a heat exchanger excellent in corrosion resistance, which is formed by cladding a sacrificial anode skin material having a composition of 0.02 to 1.5% and the balance of Al and inevitable impurities, (7) Mn: 0.8 to 1.8%, Cu: 0.1 to
One side of a core material made of an Al alloy having a composition of 1.0% and the balance of Al and unavoidable impurities is provided on one surface of the core material.
-Si or Al-Si-Zn brazing material is clad, and Mn: 0.02 to 1.5%
, Fe: 0.3 to 2.0%, Ni: 0.
1 to 1.0% of one or two of which contains A
(1) Mn: 0.8-1.8%, C: aluminum alloy clad material for heat exchangers having excellent corrosion resistance obtained by cladding a sacrificial anode skin material having a composition of l and unavoidable impurities.
u: 0.1 to 1.0%, Fe: 0.4 to 1.5%, the balance being Al having a composition consisting of Al and unavoidable impurities
An Al-Si or Al-Si-Zn brazing material is clad on one surface of a core material made of an alloy, and Mn: 0.02 to 1.5% is contained on the other surface of the core material. Further, a sacrificial anode skin material having a composition containing one or two of Fe: 0.3 to 2.0% and Ni: 0.1 to 1.0% and the balance of Al and inevitable impurities is used. Aluminum alloy clad material for heat exchanger having excellent corrosion resistance formed by cladding, (9) Mn: 0.8-1.8%, Cu: 0.1-
1.0%, Fe: 0.4 to 1.5%, Si: 0.1 to
One side of a core material made of an Al alloy having a composition of 1.0% and the balance of Al and unavoidable impurities is provided on one surface of the core material.
-Si or Al-Si-Zn brazing material is clad, and Mn: 0.02 to 1.5%
, Fe: 0.3 to 2.0%, Ni: 0.
1 to 1.0% of one or two of which contains A
aluminum alloy clad material for heat exchangers having excellent corrosion resistance obtained by cladding a sacrificial anode skin material having a composition of l and unavoidable impurities, (10) Mn: 0.8-1.8%, C
u: 0.1 to 1.0%, and further Ti: 0.05
０．２0.2%, Zr: 0.05-0.2%, one or two of which are contained, and the balance is formed on one side of a core material made of an Al alloy having a composition of Al and unavoidable impurities. Al-
An Si-based or Al-Si-Zn-based brazing material is clad and Mn: 0.02 to 1.5%
, Fe: 0.3 to 2.0%, Ni: 0.
1 to 1.0% of one or two of which contains A
(11) Mn: 0.8-1.8%, C having excellent corrosion resistance and clad with a sacrificial anode skin material having a composition of l and unavoidable impurities.
u: 0.1 to 1.0%, Fe: 0.4 to 1.5%, Ti: 0.05 to 0.2%, Zr: 0.05
０．２0.2%, one or two of which are Al
And an Al-Si-based or Al-Si-
A Zn-based brazing material is clad, and on the other side of the core material, M
n: 0.02 to 1.5%, and further Fe: 0.3
-2.0%, Ni: 0.1-1.0%, containing one or two of them, with the balance being clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities, and having excellent corrosion resistance Aluminum alloy clad material for heat exchanger, (12) Mn:
0.8-1.8%, Cu: 0.1-1.0%, Fe:
0.4-1.5%, Si: 0.1-1.0%,
Further, Ti: 0.05 to 0.2%, Zr: 0.05 to
Al-Si or Al-Si-Z is provided on one surface of a core material containing one or two of 0.2% and the balance being an Al alloy having a composition of Al and unavoidable impurities.
An n-type brazing material is clad, and the other surface of the core material is
n: 0.02 to 1.5%, and further Fe: 0.3
-2.0%, Ni: 0.1-1.0%, containing one or two of them, with the balance being clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities, and having excellent corrosion resistance Aluminum alloy clad material for heat exchanger, (13) Mn:
0.8 to 1.8%, Cu: 0.1 to 1.0%,
On one surface of a core material composed of an Al alloy having a composition consisting of Al and unavoidable impurities, an Al-Si or A
An l-Si-Zn brazing material is clad, and the other side of the core material contains Mn: 0.02 to 1.5%, and
e: 0.3 to 2.0%, Ni: one or two of 0.1 to 1.0%, and Si: 0.1 to 0.8
%, And an aluminum alloy clad material for a heat exchanger excellent in corrosion resistance obtained by cladding a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities, and (14) Mn:
0.8-1.8%, Cu: 0.1-1.0%, Fe:
An Al-Si-based or Al-Si-Zn-based brazing material is clad on one side of a core material made of an Al alloy having a composition of 0.4 to 1.5%, with the balance being Al and unavoidable impurities. Mn: 0.02 to the other surface of the core material
1.5%, Fe: 0.3-2.0%, N
i: containing one or two of 0.1 to 1.0%,
Furthermore, an aluminum alloy clad material for a heat exchanger having excellent corrosion resistance, which is formed by cladding a sacrificial anode skin material having a composition of Si: 0.1 to 0.8% and the balance of Al and inevitable impurities, (15) Mn : 0.8 to 1.8%, Cu:
0.1-1.0%, Fe: 0.4-1.5%, Si:
An Al-Si-based or Al-Si-Zn-based brazing material is clad on one surface of a core material containing 0.1 to 1.0%, the balance being an Al alloy having a composition consisting of Al and unavoidable impurities. Mn: 0.02 to the other surface of the core material
1.5%, Fe: 0.3-2.0%, N
i: containing one or two of 0.1 to 1.0%,
Further, an aluminum alloy clad material for a heat exchanger having excellent corrosion resistance, which is formed by cladding a sacrificial anode skin material having a composition of Si: 0.1 to 0.8% and the balance of Al and inevitable impurities, (16) Mn : 0.8 to 1.8%, Cu:
0.1-1.0%, and Ti: 0.05-
0.2%, Zr: 0.05 to 0.2%, one or two of which are contained, and the remainder is made of an Al alloy having a composition consisting of Al and unavoidable impurities. -S
Cladding an i-based or Al-Si-Zn-based brazing material,
The other side of the core material contains Mn: 0.02 to 1.5%, Fe: 0.3 to 2.0%, Ni: 0.1 to 0.1%
1.0% of one or two kinds, further containing Si:
An aluminum alloy clad material for a heat exchanger, which is excellent in corrosion resistance and is clad with a sacrificial anode skin material having a composition of 0.1 to 0.8%, with the balance being Al and unavoidable impurities;
(17) Mn: 0.8-1.8%, Cu: 0.1-1.0
%, Fe: 0.4 to 1.5%, and further Ti:
0.05 to 0.2%, Zr: one or two of 0.05 to 0.2% of the core material, and the balance is one of core materials made of an Al alloy having a composition of Al and unavoidable impurities. An Al-Si or Al-Si-Zn brazing material is clad on one surface, and Mn: 0.02 to
1.5%, Fe: 0.3-2.0%, N
i: containing one or two of 0.1 to 1.0%,
Furthermore, an aluminum alloy clad material for a heat exchanger having excellent corrosion resistance, which is formed by cladding a sacrificial anode skin material having a composition of Si: 0.1 to 0.8% and the balance of Al and inevitable impurities, (18) Mn : 0.8 to 1.8%, Cu:
0.1-1.0%, Fe: 0.4-1.5%, Si:
0.1-1.0%, and Ti: 0.05-
0.2%, Zr: 0.05 to 0.2%, one or two of which are contained, and the remainder is made of an Al alloy having a composition consisting of Al and unavoidable impurities. -S
Cladding an i-based or Al-Si-Zn-based brazing material,
The other side of the core material contains Mn: 0.02 to 1.5%, Fe: 0.3 to 2.0%, Ni: 0.1 to 0.1%
1.0% of one or two kinds, further containing Si:
An aluminum alloy clad material for a heat exchanger, which is excellent in corrosion resistance and is clad with a sacrificial anode skin material having a composition of 0.1 to 0.8%, with the balance being Al and unavoidable impurities;
(19) Mn: 0.8-1.8%, Cu: 0.1-1.0
%, And the other is made of Al-Si on one surface of a core material made of an Al alloy having a composition of Al and unavoidable impurities.
Or Al-Si-Zn brazing material is clad, and the other side of the core material contains Mn: 0.02-1.5%, Fe: 0.3-2.0%, Ni : 0.1 ~
1.0% or more, and further contains In:
0.005 to 0.5%, Sn: one or two of 0.005 to 0.5%, the remainder being clad with a sacrificial anode skin material having a composition of Al and unavoidable impurities. Aluminum alloy clad material for heat exchanger with excellent corrosion resistance, (20) Mn: 0.8-1.8%, Cu: 0.1-
1.0%, Fe: 0.4 to 1.5%, the remainder being A
1 and an Al-Si-based or Al-Si
-Clad a Zn-based brazing material, and on the other side of the core material,
Mn: 0.02 to 1.5%, and Fe: 0.
3 to 2.0%, Ni: one or two of 0.1 to 1.0%, and In: 0.005 to 0.5%,
Sn: An aluminum alloy for a heat exchanger excellent in corrosion resistance, comprising one or two of 0.005 to 0.5% and clad with a sacrificial anode skin material having a composition consisting of Al and inevitable impurities. Cladding material, (21) Mn: 0.8 ~
1.8%, Cu: 0.1 to 1.0%, Fe: 0.4 to
1.5%, Si: 0.1 to 1.0%, the remainder being A
1 and an Al-Si-based or Al-Si
-Clad a Zn-based brazing material, and on the other side of the core material,
Mn: 0.02 to 1.5%, and Fe: 0.
3 to 2.0%, Ni: one or two of 0.1 to 1.0%, and In: 0.005 to 0.5%,
Sn: An aluminum alloy for heat exchangers containing one or two of 0.005 to 0.5% and clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. Cladding material, (22) Mn: 0.8 ~
1.8%, Cu: 0.1 to 1.0%.
i: 0.05 to 0.2%; Zr: 0.05 to 0.2% of a core material containing one or two of 0.05% to 0.2%, and the balance being an Al alloy having a composition of Al and unavoidable impurities. An Al-Si or Al-Si-Zn brazing material is clad on one side, and Mn: 0.02
１．５1.5%, and further Fe: 0.3-2.0%,
Ni: One or two of 0.1 to 1.0%, further In: 0.005 to 0.5%, Sn: 0.0
An aluminum alloy clad material for a heat exchanger having excellent corrosion resistance, comprising one or two of the above-mentioned components and a clad of a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. 23) Mn: 0.8-1.8%, C
u: 0.1 to 1.0%, Fe: 0.4 to 1.5%, Ti: 0.05 to 0.2%, Zr: 0.05
０．２0.2%, one or two of which are Al
And an Al-Si-based or Al-Si-
Cladding a Zn-based brazing material, the other surface of the core material, M
n: 0.02 to 1.5%, and further Fe: 0.3
To 2.0%, Ni: 0.1 to 1.0%, one or two of which are further contained, and In: 0.005 to 0.5%, S
n: an aluminum alloy for a heat exchanger excellent in corrosion resistance, comprising one or two of 0.005 to 0.5% and clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. Cladding material, (24) Mn: 0.8 ~
1.8%, Cu: 0.1 to 1.0%, Fe: 0.4 to
1.5%, Si: 0.1 to 1.0%.
i: 0.05 to 0.2%; Zr: 0.05 to 0.2% of a core material containing one or two of 0.05% to 0.2%, and the balance being an Al alloy having a composition of Al and unavoidable impurities. An Al-Si or Al-Si-Zn brazing material is clad on one side, and Mn: 0.02
１．５1.5%, and further Fe: 0.3-2.0%,
Ni: One or two of 0.1 to 1.0%, further In: 0.005 to 0.5%, Sn: 0.0
An aluminum alloy clad material for a heat exchanger having excellent corrosion resistance, comprising one or two of the above-mentioned components and a clad of a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. It has features.

First, the reason why the component composition of the aluminum alloy clad material for a heat exchanger of the present invention is limited as described above will be described. (A) Core material Mn: Mn contained in the core material is Al-Mn in the core material.
It is a component that is dispersed as an intermetallic compound and improves strength without lowering corrosion resistance.
If it is less than 8%, the desired effect cannot be obtained. On the other hand, if it exceeds 1.8%, workability is deteriorated due to formation of coarse intermetallic compounds, which is not preferable. Therefore, Mn
Was determined to be 0.8 to 1.8%. A more preferred range for the Mn content is 1.0 to 1.5%.

Cu: Cu contained in the core material forms a solid solution in the matrix to improve the strength of the core material, and makes the potential of the core material noble, thereby increasing the potential difference between the sacrificial anode material and the brazing material. If the content is less than 0.1%, the desired effect cannot be obtained. On the other hand, if the content exceeds 1.0%, the melting point of the core material decreases, so that the material is easily melted during brazing. In addition, intergranular corrosion is more likely to occur, and the corrosion resistance is undesirably reduced. Therefore, the content of Cu is set to 0.1 to 1.0%. A more preferable range of the Cu content is 0.3 to 0.7%.

[0010] Fe: Fe becomes a form of corroded corrosion due to finely dispersing the Al-Fe intermetallic compound in the base material and slows down the corrosion rate. If the content is less than 0.4%, the desired effect is obtained. On the other hand, if it exceeds 1.5%, the self-corrosion of the core material increases, which is not preferable. Therefore, the content of Fe is set to 0.4 to 1.5%. F
The more preferable range of the content of e is 0.5 to 1.2%.
It is.

Si: Si has the effect of becoming an Al-Mn-Si intermetallic compound by coexisting with Mn and dispersing in a matrix or dissolving in a matrix to improve the strength of the core material. If the content is less than 0.1%, the desired effect cannot be obtained. On the other hand, if the content exceeds 1.0%, the melting point of the core material is undesirably lowered. Therefore, the content of Si is set to 0.1 to 1.0%. Si
Is more preferably in the range of 0.2 to 0.5%.

Ti, Zr: These components contained in the core material are dispersed as fine intermetallic compounds in the base material after brazing and have an effect of improving the strength of the core material. If the content is less than 0.05% Ti and less than 0.05% Zr, the desired effects cannot be obtained,
On the other hand, if the content exceeds Ti: 0.2% and Zr: 0.2%, the workability is impaired, which is not preferable. Therefore,
Ti: 0.05-0.2%, Zr: 0.05-0.2%
Determined.

(B) Sacrificial anode skin material Mn: Mn contained in the sacrificial anode skin material enhances the strength, and forms a dense and excellent adhesion film on the surface of the sacrificial anode skin material when contacted with cooling water having a pH of 9 or more. Although it is a component to be formed, if the content is less than 0.02%, the desired effect cannot be obtained. On the other hand, if the content exceeds 1.5%, processability is deteriorated due to formation of coarse intermetallic compounds. Not preferred. Therefore, the content of Mn is set to 0.02 to 1.5%.
Determined. A more preferred range for the Mn content is 0.1.
3 to 1.2%.

Fe: Fe has a large number of fine pits generated on the surface of the material starting from the finely dispersed Al-Fe intermetallic compound in order to finely disperse the Al-Fe intermetallic compound in the base material. Therefore, the corrosion depth becomes shallow, and the corrosion form becomes surface corrosion, so that deep pitting does not occur. However, if the content of Fe contained in the sacrificial anode skin material is less than 0.3%, the desired effect cannot be obtained. On the other hand, if it exceeds 2.0%, the self-corrosion of the sacrificial anode skin material increases, which is not preferable. .
Therefore, the content of Fe is set to 0.3 to 2.0%. A more preferable range of the Fe content is 0.5 to 1.0.
%.

Ni: Ni is contained in the substrate similarly to Fe.
-Many fine pits are generated on the surface of the material starting from there to disperse the Ni intermetallic compound finely, but since the number of pits is large and uniformly distributed on the surface of the material, the corrosion depth is shallow, and the corrosion form is Deep pitting does not occur because of surface corrosion. However, if the content of Ni contained in the sacrificial anode skin material is less than 0.1%, the desired effect cannot be obtained.
%, The self-corrosion of the sacrificial anode material is undesirably increased. Therefore, the content of Ni is 0.1 to
It was set to 1.0%. A more preferable range of the Ni content is 0.3 to 0.7%. Ni has the same effect as Fe, but the effect is greater for Ni than for Fe.

Si: Si becomes an Al-Mn-Si intermetallic compound by coexisting with Mn and is finely dispersed in a matrix, and becomes a starting point of pitting corrosion. Has an effect of making the surface of the sardine, but if the content is less than 0.1%, the desired effect cannot be obtained.
If the content exceeds 0.8%, the self-corrosion property is undesirably increased. Therefore, the content of Si is 0.1
０．８0.8%. A more preferred range for the Si content is 0.3-0.5%.

In, Sn: These components are necessary because they have the effect of lowering the potential of the sacrificial anode skin material, making the sacrificial anode effect on the core material more effective, and preventing pitting of the core material. However, if the content is In: 0.
If the content is less than 005% and Sn: less than 0.005%, the desired effect cannot be obtained. On the other hand, if the content exceeds 0.2% and Sn: 0.2%, the self-corrosion property is excessively increased. Absent. Therefore, the contents of In and Sn in the sacrificial anode skin material are In: 0.005 to 0.2, respectively.
%, Sn: 0.005 to 0.2%.

(C) Brazing material The brazing material used in the aluminum alloy clad material for a heat exchanger of the present invention is a common Al-Si or Al-S
It is not particularly limited as long as it is an i-Zn-based brazing material, but Si contained in the brazing material is a component that lowers the melting point and imparts fluidity. Cannot be obtained. On the other hand, if the content exceeds 15%, the fluidity is rather lowered, which is not preferable. Therefore, the content of Si in the brazing material is set to 5 to 15%. An even more preferable range of the content of Si in the brazing material is 7 to 11%. Further, the content of Zn contained in the Al-Si-Zn-based brazing material is preferably 1.0 to 5.0%.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Al having the component composition shown in Tables 1 to 3
The alloy is melted, cast to produce an ingot, and the ingot is homogenized under normal conditions, hot-rolled,
Core materials a to D made of a hot-rolled sheet having a thickness of 150 mm were prepared.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3] (The asterisks indicate values outside the scope of the invention.)

Further, an Al alloy having a component composition shown in Tables 4 and 5 was melted and cast to produce an ingot. The ingot was homogenized under ordinary conditions, and then hot-rolled to a thickness of 30 mm. A sacrificial anode skin material made of a hot rolled sheet was prepared.

[0024]

[Table 4]

[0025]

[Table 5]

On the other hand, an Al alloy having the composition shown in Table 6 is melted and cast to produce an ingot, and the ingot is subjected to hot rolling under ordinary conditions to be made of a hot-rolled sheet having a thickness of 20 mm. Materials were prepared.

[0027]

[Table 6]

The core materials a to D in Tables 1 to 3, the sacrificial anode skin material in Tables 4 to 5 and the brazing material in Table 6 are superposed in accordance with the combinations shown in Tables 7 to 10. After the cladding by hot rolling, followed by intermediate annealing, and then cold rolling, the thickness of each of them is:
The cladding materials 1 to 63 of the present invention, the comparative cladding materials 1 to 3 and the conventional cladding materials of temper H14 were prepared at a cladding ratio of 15% and 10% for a sacrificial anode skin material and a brazing material, respectively, of 0.25 mm. These clad materials 1 to 6 of the present invention
3. Each test piece was prepared using the comparative clad materials 1 to 3 and the conventional clad material.
, For 3 minutes, and then cooled at a rate of 100 ° C / min. , A heat treatment was performed assuming brazing to cool to room temperature, and then a corrosion test under the following conditions was performed.

The corrosion test _{^{1 Cl -: 100ppm, SO 4}} 2-: 300ppm, Fe
^An aqueous solution (pH: 3.0) containing ³⁺ : 50 ppm was prepared as a corrosive liquid, and the heat-treated test pieces of the clad materials 1 to 63 of the present invention, the comparative clad materials 1 to 3 and the conventional clad material were subjected to heat exchange for automobiles. Flow rate: 1.
0 m / sec. Temperature: at 80 ° C. for 8 hours after immersion, and then in a room temperature static corrosion solution for 16 hours.
The operation of adding a temperature cycle of holding for 3 hours
It was performed for 0 days, and the maximum corrosion depth from the surface of the sacrificial anode skin layer after 30 days was measured. The measurement results are shown in Tables 7 to 1.
0.

[0030] assumes the use of corrosion test 2 bad LLC Cl ^-: 100ppm, S
O ₄ ^2- : An aqueous solution containing 300 ppm was adjusted to pH 1 with NaOH.
An aqueous solution adjusted to 1 was prepared as a corrosive liquid, and the heat-treated test pieces of the clad materials 1 to 63 of the present invention, the comparative clad materials 1 to 3 and the conventional clad material were flowed at a flow rate of 1.0 m / sec.
c. The temperature at which the immersion is carried out in a corrosive solution at 80 ° C. for 8 hours, followed by a temperature cycle of immersing and holding in a static corrosive solution at room temperature for 16 hours for 60 days. The maximum corrosion depth from the surface of the sacrificial anode skin material layer was measured, and the measurement results are shown in Tables 7 to 10.

[0031]

[Table 7]

[0032]

[Table 8]

[0033]

[Table 9]

[0034]

[Table 10]

From the results shown in Tables 7 to 10, the clad materials 1 to 63 of the present invention have excellent corrosion resistance because the maximum corrosion depth from the surface is extremely small as compared with the conventional clad materials. I understand. Also, it can be seen that the comparative clad materials 1 to 3 in which the core material does not contain Cu have poor corrosion resistance or other properties.

[0036]

As described above, since the clad material of the present invention is excellent in corrosion resistance, the heat exchanger manufactured using the clad material of the present invention can be penetrated even if cooling water having a wide range of pH is used. It can be used for a long time without performing, and brings about an industrially superior effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) F28F 21/08 F28F 21/08 D

Claims (7)

[Claims] 1. A core comprising, by weight, Mn: 0.8 to 1.8% and Cu: 0.1 to 1.0%, with the balance being an Al alloy having a composition consisting of Al and unavoidable impurities. One side of the material is clad with an Al-Si-based or Al-Si-Zn-based brazing material, and the other side of the core material contains Mn: 0.02 to 1.5%, An aluminum alloy clad material for a heat exchanger having excellent corrosion resistance under an alkaline environment and an acidic environment, characterized by being clad with a sacrificial anode skin material having a composition comprising Al and inevitable impurities. 2. In% by weight, Mn: 0.8 to 1.8%, Cu: 0.1 to 1.0%, and Fe: 0.4 to 1.5%. Then, the other one side of a core material made of an Al alloy having a composition consisting of Al and unavoidable impurities is clad on one surface of an Al-Si-based or Al-Si-Zn-based brazing material, and on the other surface of the core material, Mn: 0.02 to 1.5%, and the remainder is clad with a sacrificial anode skin material having a composition consisting of Al and unavoidable impurities. Excellent aluminum alloy clad material for heat exchangers. 3. In% by weight, Mn: 0.8 to 1.8%, Cu: 0.1 to 1.0%, and Fe: 0.4 to 1.5%. Further, on one surface of a core material containing Si: 0.1 to 1.0%, and the balance being Al and an unavoidable impurity, the Al-Si-based or Al-Si- A Zn-based brazing material is clad, and a sacrificial anode skin material containing Mn: 0.02 to 1.5% on the other side of the core material and the balance consisting of Al and inevitable impurities is clad. An aluminum alloy clad material for heat exchangers having excellent corrosion resistance under alkaline and acidic environments. 4. The core material according to claim 1, 2 or 3, further comprising one or two of Ti: 0.05 to 0.2% and Zr: 0.05 to 0.2%. Al-Si or Al-S
An i-Zn-based brazing material is clad, and a sacrificial anode skin material having a composition containing Mn: 0.02 to 1.5% on the other side of the core material and the balance of Al and unavoidable impurities is clad. An aluminum alloy clad material for heat exchangers having excellent corrosion resistance in an alkaline environment and an acidic environment, which is characterized by being formed by: 5. An Al—Si-based or Al—Si—Zn-based brazing material is clad on one side of a core material made of an Al alloy having a composition according to claim 1, 2, 3, or 4, wherein the core material is provided. Mn: 0.02 to 1.5%, on one side of the other, and one of the following: Fe: 0.3 to 2.0%, Ni: 0.1 to 1.0% Or an aluminum alloy cladding for heat exchangers having excellent corrosion resistance under alkaline and acidic environments, characterized by cladding a sacrificial anode skin material having a composition of Al and unavoidable impurities containing two types. Wood. 6. An Al-Si-based or Al-Si-Zn-based brazing material is clad on one side of a core material made of an Al alloy having the composition according to claim 1, 2, 3, or 4 to form the core material. Mn: 0.02 to 1.5%, on one side of the other, and one of the following: Fe: 0.3 to 2.0%, Ni: 0.1 to 1.0% Or an alkaline environment characterized by being clad with a sacrificial anode skin material having a composition of Al and unavoidable impurities, further containing Si: 0.1 to 1.0%. Aluminum alloy clad material for heat exchangers with excellent corrosion resistance in low and acidic environments. 7. An Al—Si-based or Al—Si—Zn-based brazing material is clad on one surface of a core material made of an Al alloy having the composition according to claim 1, 2, 3, or 4 to form a core material. Mn: 0.02 to 1.5%, on one side of the other, and one of the following: Fe: 0.3 to 2.0%, Ni: 0.1 to 1.0% Or two or more, In: 0.005 to 0.2%, Sn: 0.005 to 0.2%, and one or two of the following, and the remainder is Al and inevitable impurities An aluminum alloy clad material for a heat exchanger having excellent corrosion resistance in an alkaline environment and an acidic environment, characterized by being clad with a sacrificial anode skin material having a composition of: